EP1192226B1 - Electrodeposition bath with water-soluble polyvinyl alcohol (co)polymers - Google Patents

Electrodeposition bath with water-soluble polyvinyl alcohol (co)polymers Download PDF

Info

Publication number
EP1192226B1
EP1192226B1 EP00945845A EP00945845A EP1192226B1 EP 1192226 B1 EP1192226 B1 EP 1192226B1 EP 00945845 A EP00945845 A EP 00945845A EP 00945845 A EP00945845 A EP 00945845A EP 1192226 B1 EP1192226 B1 EP 1192226B1
Authority
EP
European Patent Office
Prior art keywords
polyvinyl alcohol
parts
polymer
electrodeposition bath
groups
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP00945845A
Other languages
German (de)
French (fr)
Other versions
EP1192226A1 (en
Inventor
Hardy Reuter
Dagmar Schemschat
Karl-Heinz Grosse-Brinkhaus
Ulrich Heimann
Walter Jouck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1192226A1 publication Critical patent/EP1192226A1/en
Application granted granted Critical
Publication of EP1192226B1 publication Critical patent/EP1192226B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D13/00—Electrophoretic coating characterised by the process
    • C25D13/22—Servicing or operating apparatus or multistep processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S524/901—Electrodepositable compositions

Definitions

  • the invention relates to a new use of water-soluble Polyvinyl alcohol (co) polymers, containing a polyvinyl alcohol (co) polymer Electrocoating bath and a process for the production of coated Substrates using the electrodeposition bath.
  • Electrocoating is a well-known method of coating the surface of electrically conductive objects (compare for example: Glasurit manual paints and paints, Curt R. Vincentz Verlag, Hanover, 1984, Pages 374 to 384 and pages 457 to 462, as well as DE-A-35 18 732, DE-A-35 18 770, EP-A-0 040 090, EP-A-0 012 463, EP-A-0 259 181, EP-A-0 433 783 and EP-A-0 262 069).
  • the process is used to coat objects made of metal, especially for priming automobile bodies, or for Coating of conductive plastic used.
  • the paints used in electrodeposition coating generally contain synthetic resins containing amino groups or carboxyl groups as binders, the neutralization of the amino or carboxyl groups achieving water dispersibility.
  • Special grinding resins and optionally other non-water-dispersible constituents such as polymers, plasticizers, pigments, fillers, additives and auxiliaries can be further constituents of the electrodeposition paints.
  • the crosslinking agents used in the electrodeposition paints are either not water-dispersible or can be water-dispersible, the electrodeposition paints being externally crosslinking, or also self-crosslinking or curable with condensation.
  • the properties of the paint are influenced.
  • electrodeposition paints are known in which the addition of polymer microparticles or suspended or dispersed polymer powders is intended to favorably influence the protection against corrosion, especially on edges.
  • EP-A-0 259 181 recommends that the edges of the coated substrate be closed observed increased susceptibility to corrosion due to an inadequate to fix thick lacquer layer by adding polymer microgels, e.g. Poly (meth) acrylate copolymers in combination with ethylenically unsaturated Vinyl compounds can be part of such microgels.
  • polymer microgels e.g. Poly (meth) acrylate copolymers in combination with ethylenically unsaturated Vinyl compounds can be part of such microgels.
  • microgel dispersions based on epoxy-amine adducts are characterized by their good tolerance and high efficacy as Edge protection additives from, as described in EP 0626 000.
  • the particle sizes of such Plastic powder can significantly reduce the particle sizes of the water-dispersible synthetic resins of known electrodeposition paints exceed: the average particle diameter in JP-A-0624820 is 1 to 50 Micrometers, in DE-A-39 40 782 and EP-A-0 433 783 at 0.1 to 100 Micrometer.
  • EP-A-0 259 181, DE-B-26 50 611, EP-A-0 052 831, EP-A-0 433 783, SU-A-436890, JP-A-53094346, JP-A-79028410 and JP-A-0624820 polymer particles described leads to aqueous electrodeposition paints in some Cases to improve the edge coverage.
  • Disadvantageous side effects of adding plastic powder are one Deterioration of the wrap around the electrocoat, the adhesion to the substrate and / or to subsequent coatings, such as overcoated paint layers or PVC underbody protection, deterioration in mechanical properties, such as Flexibility, ductility, breaking and impact resistance, poorer flow properties and a drastic deterioration in the course.
  • the stability disadvantages of the paints are eliminated by incorporating copolymers with vinyl acetal, vinyl alcohol and ethylene units directly into the resins, for example. by grafting reaction, as described in DE 196 18 379.
  • the proportion is more than 10% by weight. of polymer resin is necessary to achieve adequate edge coverage.
  • the incorporation of plastic powder or microgels requires proportions in the percentage range, whereby the flow is in some cases drastically impaired.
  • im Electrodeposition paints are water-soluble cellulose ethers, such as hydroxyethyl cellulose, (EP 0640 700). The effectiveness is not permanent, however, because of the degradation of the polymer takes place.
  • Polyvinyl alcohols are widely used in paints, especially as Suspension stabilizers in the polymerization of vinyl monomers.
  • Polyvinyl alcohols as complexing agents and suspension stabilizers in the pre-treatment of iron, steel, zinc and aluminum sheets in combination with chromates or fluorine compounds is known (J 73008702, WO 9627034), in particular the electrophoretic deposition of metal suspensions, such as Aluminum (SU 738334, J-A-111201), metal oxide suspensions, such as bsw.
  • Electrocoating indicate which coatings result in all requirements in terms of edge protection and resistance to contamination, especially towards Oiling is sufficient and at the same time can be produced with little effort and has long-term stability are.
  • the invention teaches the use of a water soluble polyvinyl alcohol (co) polymers or a mixture of Polyvinyl alcohol (co) polymers as an additive in aqueous electrocoating baths.
  • Aqueous electrocoating baths contain little or no organic Solvent.
  • the term water soluble means a real dissolution process in water and not a dispersion of particulate units at the supermolecular level.
  • the polyvinyl alcohol (co) polymer is preferably used as an additive in aqueous solution prepared, if necessary with conventional paint additives, and the aqueous solution dem Electrocoating bath added.
  • additive defines that the Polyvinyl alcohol (co) polymer as a molecularly independent unit in Electrocoating bath is present and in particular not reactive in a binder, resin or the like is involved. Of course, this definition does not conclude from that the polyvinyl alcohol (co) polymer is reactive in a deposited coating is incorporated into the other components of the deposited coating.
  • polyvinyl alcohol (co) polymer denotes a random copolymer or block copolymer which contains polymer units of the general formula I, or a homopolymer which consists of polymer units of the general formula I, the polyvinyl alcohol copolymers being advantageous according to the invention, and therefore are preferred.
  • the polymer building blocks I be linked head-to-head or head-to-tail.
  • the polymer building blocks I are advantageously to a far predominant extent Head and tail linked.
  • variable R 1 stands for hydrogen atoms or for substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals.
  • alkyl radicals examples include methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.
  • Suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.
  • alkylcycloalkyl radicals examples include methylenecyclohexane, Ethylene cyclohexane or propane-1,3-diyl-cyclohexane.
  • Suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, - Propyl- or -butylcyclohex-1-yl.
  • Suitable aryl radicals are phenyl, naphthyl or biphenylyl.
  • alkylaryl radicals examples include benzyl, ethylene or propane-1,3-diylbenzene.
  • Suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl.
  • Suitable arylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, -propyl- or -Butylphen-1-yl.
  • Suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl.
  • radicals R 1 described above can be substituted.
  • electron-withdrawing or electron-donating atoms or organic radicals can be used.
  • Suitable substitutes are halogen atoms, especially chlorine and Fluorine, nitrile groups, nitro groups, partially or fully halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and Arylcycloalkyl radicals, including those mentioned above by way of example, in particular tert-butyl; Aryloxy, alkyloxy and cycloalkyloxy radicals, in particular phenoxy, Naphthoxy, methoxy, ethoxy, propxy, butyloxy or cyclohexyloxy; Arylthio, Alkylthio and cycloalkylthio radicals, in particular phenylthio, naphthylthio, Methylthio, ethylthio, propylthio, butyl
  • the radicals R 1 are predominantly hydrogen atoms, that is to say that the other radicals R 1 are only present in a minor proportion.
  • the term “subordinate portion” denotes a portion which advantageously varies the application properties profile of the polyvinyl alcohol (co) polymers, in particular their water solubility, and does not deteriorate or even completely change them.
  • Special advantages result if they change the radicals R 1 are exclusively hydrogen atoms, that is to say that the polymer building blocks I are derived from the hypothetical polyvinyl alcohol. Accordingly, polyvinyl alcohol (co) polymers which contain these polymer building blocks I are used with particular preference.
  • polyvinyl alcohol copolymers to be used according to the invention also contain, in particular, polymer building blocks of the general formula II. - [- C (R 1 ) 2 -C (R 1 ) (OC (O) R 2 ) -] - (II)
  • the radicals R 1 have the meaning given above, hydrogen atoms also being of particular advantage here and therefore being used with particular preference.
  • the radicals R 2 represent alkyl radicals with one to ten carbon atoms, preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl, particularly preferably methyl.
  • the particularly preferred polymer building blocks II are derived from vinyl acetate.
  • the polymer building blocks II can be linked head-to-head or head-to-tail.
  • the polymer building blocks II are by far predominantly head-to-tail linked.
  • these monomers are also used, they are to be used according to the invention using polyvinyl alcohol copolymers only in a minor proportion included, this term also here in the sense explained above is applied.
  • the acyclic olefins offer in particular ethylene and propylene, in particular ethylene, particular advantages and are therefore preferably used if necessary.
  • Polyvinyl alcohol (co) polymers have a degree of polymerization of 100 to 20,000, preferably 200 to 15,000, particularly preferably 300 to 12,000 and in particular 400 up to 10,000.
  • the content of polymer building blocks I is advantageously in the Polyvinyl alcohol copolymers at 50 to 99.9, preferably 60 to 99.9, especially preferably 70 to 99 and in particular 80 to 99 mol%.
  • the polyvinyl alcohol copolymers offer the particularly advantageous polymer building blocks I and II contain very special ones Advantages and are therefore used very particularly preferably according to the invention. These polyvinyl alcohol copolymers are also known in the art for short Called polyvinyl alcohols.
  • polyvinyl alcohols are not by direct Polymerization processes are accessible, but are based on polymer analogs Reactions produced by hydrolysis of polyvinyl acetate.
  • Particularly advantageous Commercial polyvinyl alcohols have molecular weights of 10,000 to 500,000 Daltons, preferably 15,000 to 320,000 Daltons and especially 20,000 to 300,000 daltons.
  • Very particularly advantageous, commercially available polyvinyl alcohols have a degree of hydrolysis of 98 to 99 or 87 to 89 mol%.
  • the vinyl alcohol content can be determined, for example, indirectly via the DIN ester number 53401 determine, namely by the remaining proportion of vinyl acetate after the Hydrolysis is determined by means of the ester number.
  • ATL anodic
  • KTL cathodic
  • ETL electrodeposition paint baths
  • Electroposition baths are aqueous coating materials (ETL) with a Solids content of in particular 5 to 30% by weight.
  • crosslinking agents (B) and / or their functional groups (b1) ready in the binder (A) incorporated one speaks of self-crosslinking.
  • the binders (A) come as complementary functional groups (a2) preferably thio, amino, hydroxyl, carbamate, allophanate, carboxy, and / or (meth) acrylate groups, but in particular hydroxyl groups, and as complementary functional groups (b1) preferably anhydride, carboxy, Epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, amino, Hydroxy and / or beta-hydroxyalkylamide groups, but especially blocked Isocyanate groups into consideration.
  • complementary functional groups (a2) preferably thio, amino, hydroxyl, carbamate, allophanate, carboxy, and / or (meth) acrylate groups, but in particular hydroxyl groups
  • complementary functional groups (b1) preferably anhydride, carboxy, Epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, amino, Hydroxy and / or beta-hydroxyalkylamide groups,
  • the binders (A) with functional groups (a11) are in cathodic separable electrodeposition paints (KTL) are used, whereas the binders (A) with functional groups (a12) used in anodic electrodeposition paints (ATL) will.
  • Suitable functional groups (a11) to be used according to the invention those by neutralizing agents and / or quaternizing agents in cations are primary, secondary or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups, especially tertiary ones Amino groups or secondary sulfide groups.
  • Suitable cationic groups to be used according to the invention (a11) are primary, secondary, tertiary or tertiary sulfonium groups or quaternary Phosphonium groups, preferably quaternary ammonium groups or quaternary Ammonium groups, tertiary sulfonium groups, but especially quaternary groups Ammonium groups.
  • Suitable functional groups (a12) to be used according to the invention which can be converted into anions by neutralizing agents Carboxylic acid, sulfonic acid or phosphonic acid groups, in particular Carboxylic acid groups.
  • Suitable anionic groups to be used according to the invention (a12) are carboxylate, sulfonate or phosphonate groups, in particular Carboxylate groups.
  • the selection of the groups (a11) or (a12) is to be made so that no disturbing Reactions with the functional groups (a2) with the crosslinking agents (B) can react, are possible.
  • the person skilled in the art can therefore make the selection in a simpler manner Wise, based on their expertise.
  • Suitable neutralizing agents for functional ones convertible to cations Groups (a11) are inorganic and organic acids such as sulfuric acid, Hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, Dimethylolpropionic acid or citric acid, especially formic acid, acetic acid or lactic acid.
  • Suitable neutralizing agents for convertible into anions functional groups (a12) are ammonia, ammonium salts such as, for example
  • Ammonium carbonate or ammonium hydrogen carbonate as well as amines, e.g. Trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, Triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, Triethanolamine and the like.
  • amines e.g. Trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, Triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, Triethanolamine and the like.
  • the amount of neutralizing agent is chosen so that 1 to 100 equivalents, preferably 50 to 90 equivalents of the functional Groups (a11) or (a12) of the binder (b1) are neutralized.
  • Suitable binders (A) for ATL are from patent DE-A-2824 418 known. These are preferably polyester, epoxy resin ester, Poly (meth) acrylates, maleic oils or polybutadiene oils with a weight average Molecular weight from 300 to 10,000 Daltons and an acid number from 35 to 300 mg KOH / g.
  • KTL examples of suitable KTL can be found in the patents EP-A-0 082 291, EP-A-0 234 395, EP-A-0 227 975, EP-A-0 178 531, EP-A-333 327, EP-A-0 310 971, EP-A-0 456 270, US-A-3,922,253, EP-A-0 261 385, EP-A-0 245 786, DE-A-33 24 211, EP-A-0 414 199 or EP-A-476 514 known.
  • These are preferably primary, secondary, tertiary or quaternary amino or ammonium groups and / or resins (A) containing tertiary sulfonium groups and having amine numbers preferably between 20 and 250 mg KOH / g and a weight average Molecular weight from 300 to 10,000 daltons.
  • A tertiary sulfonium groups and having amine numbers preferably between 20 and 250 mg KOH / g and a weight average Molecular weight from 300 to 10,000 daltons.
  • KTL and the corresponding electrodeposition baths preferably used.
  • the EDL preferably contain crosslinking agents (B).
  • Suitable crosslinking agents (B) are blocked organic ones Polyisocyanates, in particular blocked so-called paint polyisocyanates, with aliphatically, cycloaliphatically, araliphatically and / or aromatically bound, blocked isocyanate groups.
  • Polyisocyanates with 2 to 5 isocyanate groups are preferred for their preparation per molecule and with viscosities from 100 to 10,000, preferably 100 to 5000 and in particular 100 to 2000 mPas (at 23 ° C) are used.
  • the Polyisocyanates in the customary and known manner are hydrophilic or hydrophobic be modified.
  • polyisocyanates examples include, for example, in "Methods of organic chemistry ", Houben-Weyl, Volume 14/2, 4th edition, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70, and by W. Siefken, Liebigs Annalen der Chemie, Volume 562, pages 75 to 136.
  • the Polyurethane prepolymers containing isocyanate groups, which are produced by the reaction of polyols can be prepared with an excess of polyisocyanates and the are preferably of low viscosity.
  • polyisocyanates are isocyanurate, biuret, allophanate, Iminooxadiazinedione, urethane, urea and / or uretdione groups
  • polyisocyanates containing urethane groups are, for example by reacting part of the isocyanate groups with polyols, e.g.
  • Trimethylolpropane and glycerol are preferably aliphatic or cycloaliphatic polyisocyanates, especially hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, Dicyclohexylmethane-2,4'-diisocyanate, Dicyclohexylmethane-4,4'-diisocyanate or 1,3-bis (isocyanatomethyl) cyclohexane (BIC), diisocyanates derived from dimer fatty acids such as those under the The trade name DDI 1410 is sold by the Henkel company, 1,8-diisocyanato-4-isocyanatomethyl octane, 1,7-diisocyanato-4-isocyanatomethylheptane or 1-isocyanato-2- (3
  • suitable crosslinking agents (B) are all known aliphatic and / or cycloaliphatic and / or aromatic polyepoxides, for example based on bisphenol-A or bisphenol-F.
  • Suitable as polyepoxides are, for example, also those commercially available under the names Epikote® der Shell, Denacol® from Nagase Chemicals Ltd., Japan Polyepoxides, such as Denacol EX-411 (pentaerythritol polyglycidyl ether), Denacol EX-321 (trimethylolpropane polyglycidyl ether), Denacol EX-512 (polyglycerol polyglycidyl ether) and Denacol EX-521 (polyglycerol polyglycidyl ether).
  • TACT alkoxycarbonylamino triazines
  • B crosslinking agents
  • tris (alkoxycarbonylamino) triazines (B) examples are in the US-A-4,939,213, US-A-5,084,541 or EP-A-0 624 577 are described.
  • methyl-butyl mixed esters and the butyl-2-ethylhexyl mixed esters are advantageous and the butyl esters. These have the advantage over the pure methyl ester better solubility in polymer melts and also less prone to Crystallize.
  • crosslinking agents (B) are amino resins, for example melamine, guanamine, benzoguanamine or urea resins. Included The customary and known amino resins are also suitable, their Methylol and / or methoxymethyl groups e.g. T. by means of carbamate or Allophanate groups are defunctionalized. Crosslinking agents of this type are used in US-A-4 710 542 and EP-B-0 245 700 and in the article by B. Singh et al. "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry "in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193-207.
  • crosslinking agents (B) are beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N'-tetrakis (2-hydroxypropyl) adipamide.
  • suitable crosslinking agents (B) are compounds with on average at least two groups capable of transesterification, for example Reaction products of malonic acid diesters and polyisocyanates or of esters and partial esters of polyhydric alcohols of malonic acid with monoisocyanates, such as them European Patent EP-A-0 596 460;
  • the amount of crosslinking agents (B) in the coating material of the invention or ETL can vary widely and is based in particular on the one hand Functionality of the crosslinking agent (B) and on the other hand according to the number of im Binder (A) existing crosslinking functional groups (a2) and after the network density that you want to achieve.
  • the skilled person can therefore determine the amount the crosslinking agent (B) on the basis of his general technical knowledge, if appropriate determine with the help of simple, orienting experiments.
  • the crosslinking agent (B) in the coating material of the invention in one Amount of 5 to 60% by weight, particularly preferably 10 to 50% by weight and in particular 15 to 45 wt .-%, each based on the solids content of the coating material according to the invention contain.
  • crosslinking agent (B) and binder (A) it is recommended to use the further to choose the amounts of crosslinking agent (B) and binder (A) so that in the coating material of the invention the ratio of functional Groups (b1) in the crosslinking agent (B) and functional groups (a2) in Binder (A) between 2: 1 to 1: 2, preferably 1.5: 1 to 1: 1.5, especially preferably 1.2: 1 to 1: 1.2 and in particular 1.1: 1 to 1: 1.1.
  • the invention finally teaches a method for painting electrically conductive Substrates in which (1) the electrically conductive substrate in an electrodeposition bath is immersed as described above, (2) the substrate as a cathode or anode, preferably as a cathode, is switched on, (3) by direct current Film is deposited on the substrate, (4) the painted substrate from the Electrodeposition paint bath is removed, (5) the deposited paint film is baked and, (6) optionally, following step (5) a filler, a stone chip protection paint and a solid top coat or, alternatively, a base coat and a clear coat are applied and are baked, the basecoat and the clearcoat preferably after Wet-on-wet process can be applied and baked.
  • the temperature is kept at 60 ° C. for a further 60 minutes and is reduced NCO equivalent weight of 1120 g / eq determined (based on solids).
  • NCO equivalent weight 1120 g / eq determined (based on solids).
  • 933 parts are melted Trimethylolpropane added at such a rate that a Product temperature of 100 ° C is not exceeded.
  • the end of the addition one leaves react for a further 60 min. There are no NCO groups in the subsequent control more verifiable. It is cooled to 65 ° C. and diluted at the same time 965 parts of n-butanol and 267 parts of methyl isobutyl ketone.
  • the solids content is 70.1% (1 h at 130 ° C.).
  • the temperature is kept at 60 ° C. for a further 60 minutes and is reduced NCO equivalent weight of 887 g / eq determined (based on solids).
  • NCO equivalent weight 887 g / eq determined (based on solids).
  • 1293 parts are melted Trimethylolpropane added at such a rate that a Product temperature of 100 ° C is not exceeded.
  • the solids content is 80.5% (1 h at 130 ° C).
  • K2000 polyether, Byk Chemie / Germany
  • Plastilit® 3060 75 minutes after the addition of the amine, 903 parts of Plastilit® 3060 are used (Propylene glycol compound, BASF / Germany), diluted with 522 parts Propylene glycol phenyl ether (mixture of 1-phenoxy-2-propanol and 2-phenoxy-1-propanol, BASF / Germany), and at the same time cools down rapidly to 95 ° C. After 10 minutes, 14821 parts of the reaction mixture are placed in a dispersing vessel convicted. There, 474 parts of lactic acid (88% in Water), dissolved in 7061 parts of deionized water. Then 20 min homogenized before using a further 12600 parts of deionized water in small Portions being further diluted.
  • the volatile solvents are removed by distillation in vacuo and then replaced in the same amount by deionized water.
  • the dispersion (A / B1) has the following key figures: Solids content 33.8% (1 hour at 130 ° C) 29.9% (1/2 hour at 180 ° C) Base content 0.71 milliequivalents / g solid (130 ° C) Acidity 0.36 milliequivalents / g solid (130 ° C) pH 6.3 Particle size 116 nm (Mass mean from photon correlation spectroscopy)
  • binder dispersion (A / B2) is produced in a completely analogous manner to Binder dispersion (A / B1), however, are used immediately after dilution with Propylene glycol phenyl ether 378 parts of K-KAT® XP 348 (bismuth 2-ethylhexanoate; 25% bismuth, King Industries, USA) with stirring in the organic stage mixed in. After cooling, completely analogous to (A / B1) 14821 parts of the Reaction mixture dispersed:
  • the dispersion (A / B2) has the following key figures: Solids content 33.9% (1 hour at 130 ° C) 30.1% (1/2 hour at 180 ° C) Base content 0.74 milliequivalents / g solid (130 ° C) Acidity 0.48 milliequivalents / g solid (130 ° C) pH 5.9 Particle size 189 nm (Mass mean from photon correlation spectroscopy)
  • reaction mixture After 10 minutes, the entire reaction mixture is transferred to a dispersing vessel. There, 609 parts of lactic acid (88% in water) and 152 parts of emulsifier mixture (mixture of 1 part butyl glycol and 1 part of a tertiary acetylene glycol (Surfynol 104, Air Products / USA)), dissolved in 30266 parts of deionized, are added in portions with stirring Water, too.
  • lactic acid 88% in water
  • emulsifier mixture mixture of 1 part butyl glycol and 1 part of a tertiary acetylene glycol (Surfynol 104, Air Products / USA)
  • the volatile solvents are removed by distillation in vacuo and then replaced in the same amount by deionized water.
  • the dispersion (A / B3) has the following key figures: Solids content 37.0% (1 hour at 130 ° C) 34.1% (1/2 hour at 180 ° C) Base content 0.53 milliequivalents / g solid (130 ° C) Acidity 0.32 milliequivalents / g solid (130 ° C) pH 6.6 Particle size 150 nm (Mass mean from photon correlation spectroscopy)
  • the viscous solution is stabilized against bacterial attack with 9 parts of Parmetol® K40 (Schülke and Mayr / Germany).
  • the solids content of the solution is 5.0% (1 h at 130 ° C.).
  • the product formed was characterized: Poly (vinyl alcohol-co-vinyl acetate-co-ethylene): Weight average molar mass 215,000 daltons Polyvinyl alcohol content 83.3% Polyvinyl acetate content 9.5% Polyethylene content 7.2%
  • the solids content of the solution is 5.0% (1 h at 130 ° C.).
  • an organic-aqueous grinding resin solution is used prepared by placing 2598 Parts of bisphenol A diglycidyl ether (epoxy equivalent weight (EEW) 188 g / eq), 787 Parts of bisphenol-A, 603 parts of dodecylphenol and 206 parts of butylglycol in Presence of 4 parts triphenylphosphine at 130 ⁇ C up to an EEW of 865 g / eq can react.
  • EW epoxy equivalent weight
  • the resin solution is used directly for paste production.
  • a pigment paste PI which is stable to segregation is obtained. Solids content 60.0% (1/2 hour at 180 ° C)
  • An organic-aqueous sulfonium grating resin solution is prepared by in the first stage in a stainless steel reaction vessel 2632 parts of bisphenol A diglycidyl ether (Epoxy equivalent weight (EEW) 188 g / eq), 985 parts bisphenol-A, 95 parts of nonylphenol in the presence of 1 part of triphenylphosphine at 130 ° C to reacts to an EEW of 760 g / eq.
  • EW epoxy equivalent weight
  • 985 parts bisphenol-A 985 parts of nonylphenol in the presence of 1 part of triphenylphosphine at 130 ° C to reacts to an EEW of 760 g / eq.
  • 996 Share 2-butoxypropanol the temperature is lowered to 80 ° C.
  • the reaction is complete when the acid number is less than 5 (mg KOH per g Solid). Then 10541 parts of deionized water are gradually added.
  • the resin solution is used directly for paste production.
  • the acid number is less than 1 (mg KOH per g of solid), it is 1457 parts Butyl glycol dissolved.
  • the resin solution is used directly for paste production.
  • a pigment paste (P2) which is stable to segregation is obtained. Solids content 61.5% (1/2 hour at 180 ° C)
  • Electroposition paints consist of mixtures of an aqueous dispersion (A / B) and deionized water. The resulting mixtures are added to the pigment paste (P) added with stirring in designated cases.
  • the aqueous solutions of polyvinyl alcohol (co) polymers (D) can be incorporated by adding to the binder dispersion (A / B) or pigment paste (P) with stirring, or by subsequent addition to the binder-paste mixture, as in the present case.
  • Gray pigmented electrodeposition paints based on the binder dispersion (A / B1) and the pigment paste (P1) Electrodeposition paint Comparative experiment V1 example 1
  • Example 2 Polyvinyl alcohol (co) polymer 0 ppm 600 ppm 600 ppm Parts by weight (parts) Binder disp. (A / B1) 491 491 491 Pigment paste (P1) 120 120 120 Deion. water 389 377 377 Solution of the polyvinyl alcohol (co) polym.
  • the deposited paint film is rinsed off with deionized water and 20 min Baked in for a long time at 180 ° C. The baked paint films thus obtained were checked.
  • the specified layer thicknesses are to be understood as dry film thicknesses.
  • Test results of electrocoating baths based on the binder dispersions (A / B1) and (A / b2) with and without pigment paste (P1) Electrocoating baths Pigmented gray Unpigmented (clear coat) Examples (see Point 6; Tab. 1 and 2) V1 1 2 V2 3 4th Binder dispersion (A / B1) dito dito (STARTING AT 2)*) dito dito Pigment paste (P1) dito dito - - - PVAl-CP solution (1) - (D1) (D2) - (D1) (D2) Go PVAI copolymes. in bath (2), ppm 0 600 600 0 2000 2000 Deposition on zinc phosphate. Steel tested.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemically Coating (AREA)

Abstract

The invention relates to the use of a water-soluble polyvinyl alcohol (co)polymer or a mixture of polyvinyl alcohol (co)polymers as additives in aqueous electrodeposition baths, to electrodeposition baths comprising a polyvinyl alcohol (co)polymer, and to a method of coating an electrically conductive substrate.

Description

Die Erfindung betrifft eine neue Verwendung von wasserlöslichen Polyvinylalkohol(co)polymeren, ein Polyvinylalkohol(co)polymere enthaltendes Elektrotauchlackbad sowie ein verfahren zur Herstellung beschichteter Substrate unter verwendung des Elektrotauchbades.The invention relates to a new use of water-soluble Polyvinyl alcohol (co) polymers, containing a polyvinyl alcohol (co) polymer Electrocoating bath and a process for the production of coated Substrates using the electrodeposition bath.

Die Elektrotauchlackierung ist ein hinreichend bekanntes Verfahren zur Beschichtung der Oberfläche elektrisch leitender Gegenstände (vergleiche dazu beispielsweise: Glasurit Handbuch Lacke und Farben, Curt R. Vincentz Verlag, Hannover, 1984, Seiten 374 bis 384 und Seiten 457 bis 462, sowie DE-A-35 18 732, DE-A-35 18 770, EP-A-0 040 090, EP-A-0 012 463, EP-A-0 259 181, EP-A-0 433 783 und EP-A-0 262 069). Das Verfahren wird zur Beschichtung von Objekten aus Metall, insbesondere zur Grundierung von Automobilkarosserien, oder auch zur Beschichtung leitfähiger Kunststoff eingesetzt.Electrocoating is a well-known method of coating the surface of electrically conductive objects (compare for example: Glasurit manual paints and paints, Curt R. Vincentz Verlag, Hanover, 1984, Pages 374 to 384 and pages 457 to 462, as well as DE-A-35 18 732, DE-A-35 18 770, EP-A-0 040 090, EP-A-0 012 463, EP-A-0 259 181, EP-A-0 433 783 and EP-A-0 262 069). The process is used to coat objects made of metal, especially for priming automobile bodies, or for Coating of conductive plastic used.

Die bei der Elektrotauchlackierung verwendeten Lacke enthalten als Bindemittel in der Regel aminogruppen- oder carboxylgruppenhaltige Kunstharze, wobei durch die Neutralisation der Amino- oder Carboxylgruppen eine Wasserdipergierbarkeit erzielt wird. Spezielle Anreibeharze und gegebenenfalls weitere nicht wasserdispergierbare Bestandteile wie Polymere, Weichmacher, Pigmente, Füllstoffe, Additive und Hilfsstoffe können weitere Bestandteile der Elektrotauchlacke sein. Die in den Elektrotauchlacken eingesetzten Vernetzungsmittel sind entweder nicht wasserdispergierbar oder können wasserdispergierbar sein, wobei die Elektrotauchlacke fremdvernetzend, oder auch selbstvernetzend oder unter Kondensation härtbar sind.
Durch Modifikation der Bindemittel, Auswahl der Vernetzer und Variation der Zusammensetzung der Bestandteile des Elektrotauchlacks werden die Eigenschaften der Lackierung, wie z.B. Korrosionsschutz, Haftung und Verlauf beeinflußt. So sind insbesondere Elektrotauchlacke bekannt, bei denen durch Zusatz von PolymerMikroteilchen oder suspendierten bzw. eindispergierten Polymerpulvern der Korrosionsschutz, speziell an Kanten, der Verlauf günstig beeinflußt werden soll.The paints used in electrodeposition coating generally contain synthetic resins containing amino groups or carboxyl groups as binders, the neutralization of the amino or carboxyl groups achieving water dispersibility. Special grinding resins and optionally other non-water-dispersible constituents such as polymers, plasticizers, pigments, fillers, additives and auxiliaries can be further constituents of the electrodeposition paints. The crosslinking agents used in the electrodeposition paints are either not water-dispersible or can be water-dispersible, the electrodeposition paints being externally crosslinking, or also self-crosslinking or curable with condensation.
By modifying the binding agent, selecting the crosslinking agent and varying the composition of the constituents of the electrodeposition paint, the properties of the paint, such as corrosion protection, adhesion and flow, are influenced. In particular, electrodeposition paints are known in which the addition of polymer microparticles or suspended or dispersed polymer powders is intended to favorably influence the protection against corrosion, especially on edges.

So wird in der EP-A-0 259 181 empfohlen, die an Kanten des lackierten Substrats zu beobachtende erhöhte Anfälligkeit gegenüber Korrosion aufgrund einer unzureichend dicken Lackschicht durch Zusatz von Polymer-Mikrogelen zu beheben, wobei z.B. Poly(meth)acrylat-Copolymerisate in Kombination mit ethylenisch ungesättigten Vinylverbindungen Bestandteil solcher Mikrogele sein können.For example, EP-A-0 259 181 recommends that the edges of the coated substrate be closed observed increased susceptibility to corrosion due to an inadequate to fix thick lacquer layer by adding polymer microgels, e.g. Poly (meth) acrylate copolymers in combination with ethylenically unsaturated Vinyl compounds can be part of such microgels.

Nachträglich zusetzbare Mikrogel-Dispersionen auf Basis von Epoxy-Amin-Addukten zeichnen sich durch ihre gute Verträglichkeit und hohe Wirsamkeit als Kantenschutz-Additive aus, wie in EP 0626 000 beschrieben.Subsequently addable microgel dispersions based on epoxy-amine adducts are characterized by their good tolerance and high efficacy as Edge protection additives from, as described in EP 0626 000.

In DE-B-26 50 611, EP-A-0 052 831, DE-A-39 40 782, EP-A-0 433 783, SU-A-436890, JP-A-53094346, JP-A-79028410 und JP-A-0624820 werden Elektrotauchlack-Beschichtungsmittel mit suspendierbaren oder eindispergierbaren Kunststoffpulvern beschrieben, welche überwiegend frei von ionischen Gruppen sind, gegebenenfalls beim Einbrennen schmelzen können, unvernetzt oder vernetzt sind, wobei die Beschichtungsmittel zusätzlich die für Elektrotauchlackierungen typischen wasserdispergierbaren Kunstharze enthalten. Die Teilchengrößen solcher Kunststoffpulver können hierbei deutlich die Teilchengrößen der wasserdispergierbaren Kunstharze bekannter Elektrotauchlacke überschreiten: der durchschnittliche Teilchendurchmesser in der JP-A-0624820 liegt bei 1 bis 50 Mikrometer, in der DE-A-39 40 782 bzw. EP-A-0 433 783 bei 0,1 bis 100 Mikrometer. In DE-B-26 50 611, EP-A-0 052 831, DE-A-39 40 782, EP-A-0 433 783, SU-A-436890, JP-A-53094346, JP-A-79028410 and JP-A-0624820 are used Electrocoating agents with suspendable or dispersible Plastic powders described, which are predominantly free from ionic groups, may melt during stoving, are uncrosslinked or crosslinked, the coating agents additionally being those typical for electrocoating contain water-dispersible synthetic resins. The particle sizes of such Plastic powder can significantly reduce the particle sizes of the water-dispersible synthetic resins of known electrodeposition paints exceed: the average particle diameter in JP-A-0624820 is 1 to 50 Micrometers, in DE-A-39 40 782 and EP-A-0 433 783 at 0.1 to 100 Micrometer.

Der Zusatz der in den EP-A-0 259 181, DE-B-26 50 611, EP-A-0 052 831, EP-A-0 433 783, SU-A-436890, JP-A-53094346, JP-A-79028410 und JP-A-0624820 beschriebenen Polymerteilchen zu wäßrigen Elektrotauchlacken führt in manchen Fällen zu Verbesserung der Kantenabdeckung. Dahingegen ist der Korrosionsschutz der abgeschiedenen Elektrotauchlackfilme, speziell an den Kanten, trotz der verbesserten Kantenabdeckung unzureichend.The addition of those in EP-A-0 259 181, DE-B-26 50 611, EP-A-0 052 831, EP-A-0 433 783, SU-A-436890, JP-A-53094346, JP-A-79028410 and JP-A-0624820 polymer particles described leads to aqueous electrodeposition paints in some Cases to improve the edge coverage. In contrast, the corrosion protection of the deposited electrocoat films, especially at the edges, despite the Improved edge coverage inadequate.

Nachteilige Nebeneffekte der Zugabe von Kunststoffpulver sind eine Verschlechterung des Umgriffs der Elektrotauchlacke, der Haftung zum Substrat und/oder zu nachfolgenden Beschichtungen, wie überlackierte Lackschichten oder PVC-Unterbodenschutz, Verschlechterung der mechanischen Eigenschaften, wie Flexibilität, Dehnbarkeit, Bruch- und Schlagfestigkeit, schlechtere Fließeigenschaften und eine drastische Verschlechterung des Verlaufs.Disadvantageous side effects of adding plastic powder are one Deterioration of the wrap around the electrocoat, the adhesion to the substrate and / or to subsequent coatings, such as overcoated paint layers or PVC underbody protection, deterioration in mechanical properties, such as Flexibility, ductility, breaking and impact resistance, poorer flow properties and a drastic deterioration in the course.

Ein weiterhin wesentlicher Nachteil der in den Patentschriften EP-A-0 259 181, DE-B-26 50 611, EP-A-0 052 831, EP-A-0 433 783, SU-A-436890, JP-A-53094346, JP-A-79028410, JP-A-0624820, SU-A-661637, SU-A-998592 und SU-A-310952 beschriebenen wäßrigen und nicht-wäßrigen Formulierungen ist die mangelhafte Stabilität der Lacke, die zur Sedimentation neigen. Dabei kann es in wäßrigen Elektrotauchlacken zur massiven Belegung der Ultrafiltrationsmembran mit grobteiligen Kunststoffteilchen kommen.Another major disadvantage of the patent specifications EP-A-0 259 181, DE-B-26 50 611, EP-A-0 052 831, EP-A-0 433 783, SU-A-436890, JP-A-53094346, JP-A-79028410, JP-A-0624820, SU-A-661637, SU-A-998592 and SU-A-310952 aqueous and non-aqueous formulations described is the deficient one Stability of paints that tend to sediment. It can be in aqueous Electrodeposition paints for massive coverage of the ultrafiltration membrane with coarse plastic particles come.

Die Stabilitätsnachteile der Lacke werden behoben, indem Copolymerisate mit Vinylacetal-, Vinylalkohol- und Ethyleneinheiten direkt in die Harze eingebunden werden, bsw. durch Pfropfreaktion, wie in DE 196 18 379 beschrieben.
Dabei ist ein Anteil über 10 Gew.-%. von Polymerharz notwendig, um eine ausreichende Kantenabdeckung zu erzielen.
Die Einarbeitung von Kunststoffpulver oder Mikrogelen erfordert Anteile im Prozentbereich, wobei der Verlauf z.T. drastisch verschlechtert wird. The stability disadvantages of the paints are eliminated by incorporating copolymers with vinyl acetal, vinyl alcohol and ethylene units directly into the resins, for example. by grafting reaction, as described in DE 196 18 379.
The proportion is more than 10% by weight. of polymer resin is necessary to achieve adequate edge coverage.
The incorporation of plastic powder or microgels requires proportions in the percentage range, whereby the flow is in some cases drastically impaired.

Wesentlich wirkungsvoller, auch bei geringen Konzentrationen wie 500 ppm, im Elektrotauchlack sind wasserlösliche Celluloseether, wie Hydroxyethylcellulose, (EP 0640 700). Die Wirksamkeit ist aber nicht von Dauer, da ein Abbau des Polymeren stattfindet.Much more effective, even at low concentrations such as 500 ppm, im Electrodeposition paints are water-soluble cellulose ethers, such as hydroxyethyl cellulose, (EP 0640 700). The effectiveness is not permanent, however, because of the degradation of the polymer takes place.

Polyvinylalkohole werden mannigfaltig in Lacken eingesetzt, insbesondere als Suspensionsstabilisatoren bei der Polymerisation von Vinylmonomeren. Während der Einsatz von Polyvinylalkoholen als Komplexbildner und Suspensionsstabilisator in der Vorbehandlung von Eisen-, Stahl, Zink- und Aluminiumblechen in Kombination mit Chromaten bzw. Fluorverbindungen bekannt ist (J 73008702, WO 9627034), insbesondere die elektrophoretische Abscheidung von Metallsuspensionen, wie Aluminium (SU 738334, J-A-111201), Metalloxid-Suspensionen, wie bsw. Chrom-, Aluminium-, Titan- und Zirkoniumoxid (J-A-111201, SU 493817), Metallsalz-Suspensionen, wie Blei-, Zink- oder Kupfersalzen (SU 436890, SU 511392, SU 054452, WO 9208168), sowie direkter Abscheidung von Metallen, wie Blei (SU 321265), beschränkt sich der direkte Einsatz in Elektrotauchlacken auf eine nachträgliche Behandlung des abgeschiedenen Films durch Kontakt mit einer wäßrigen Polyvinylalkohol-Lösung und anschließender Einbrennung. Durch diese nachträgliche Behandlung wird ein mattierender Effekt (JP 56044799) erzielt, bzw. Oberflächendefekte, wie Krater, verringert (DE 4303787).Polyvinyl alcohols are widely used in paints, especially as Suspension stabilizers in the polymerization of vinyl monomers. During the Use of polyvinyl alcohols as complexing agents and suspension stabilizers in the pre-treatment of iron, steel, zinc and aluminum sheets in combination with chromates or fluorine compounds is known (J 73008702, WO 9627034), in particular the electrophoretic deposition of metal suspensions, such as Aluminum (SU 738334, J-A-111201), metal oxide suspensions, such as bsw. Chrome-, Aluminum, titanium and zirconium oxide (J-A-111201, SU 493817), metal salt suspensions, such as lead, zinc or copper salts (SU 436890, SU 511392, SU 054452, WO 9208168), as well as direct deposition of metals such as lead (SU 321265), direct use in electrodeposition paints is limited to one subsequent treatment of the deposited film by contact with a aqueous polyvinyl alcohol solution and subsequent stoving. Through this subsequent treatment creates a matting effect (JP 56044799) or Surface defects such as craters are reduced (DE 4303787).

Demgegenüber liegt der Erfindung das technische Problem zugrunde, ein Elektrotauchlackbad anzugeben, welches Überzüge ergibt, die allen Anforderungen hinsichtlich Kantenschutz und Kontaminationsfestigkeit, insbesondere gegenüber Ölen, genügen und gleichzeitig mit wenig Aufwand herstellbar und langzeitstabil sind.In contrast, the invention is based on the technical problem, a Electrocoating indicate which coatings result in all requirements in terms of edge protection and resistance to contamination, especially towards Oiling is sufficient and at the same time can be produced with little effort and has long-term stability are.

Zur Lösung dieses technischen Problems lehrt die Erfindung die Verwendung eines wasserlöslichen Polyvinylalkohol(co)polymers oder einer Mischung von Polyvinylalkohol(co)polymeren als Additiv in wäßrigen Elektrotauchlackbädern.To solve this technical problem, the invention teaches the use of a water soluble polyvinyl alcohol (co) polymers or a mixture of Polyvinyl alcohol (co) polymers as an additive in aqueous electrocoating baths.

Wäßrige Elektrotauchlackbäder enthalten nur wenig oder gar keine organischen Lösungsmittel.Aqueous electrocoating baths contain little or no organic Solvent.

Der Ausdruck wasserlöslich meint einen echten Lösungsvorgang in Wasser und nicht eine Dispersion von partikulären Einheiten auf supermolekularer Ebene. Vorzugsweise wird das Polyvinylalkohol(co)polymer in wäßriger Lösung als Additiv zubereitet, ggf. mit üblichen Lackzusatzstoffen, und die wäßrige Lösung dem Elektrotauchlackbad zugegeben. Der Ausdruck "Additiv" definiert, daß das Polyvinylalkohol(co)polymer als molekular selbstständige Einheit im Elektrotauchlackbad vorliegt und insbesondere nicht reaktiv in ein Bindemittel, Harz oder dergleichen eingebunden ist. Diese Definition schließt selbstverständlich nicht aus, daß das Polyvinylalkohol(co)polymer in einem abgeschiedenen Überzug reaktiv in die weiteren Bestandteile des abgeschiedenen Überzuges eingebunden wird.The term water soluble means a real dissolution process in water and not a dispersion of particulate units at the supermolecular level. The polyvinyl alcohol (co) polymer is preferably used as an additive in aqueous solution prepared, if necessary with conventional paint additives, and the aqueous solution dem Electrocoating bath added. The term "additive" defines that the Polyvinyl alcohol (co) polymer as a molecularly independent unit in Electrocoating bath is present and in particular not reactive in a binder, resin or the like is involved. Of course, this definition does not conclude from that the polyvinyl alcohol (co) polymer is reactive in a deposited coating is incorporated into the other components of the deposited coating.

Im Rahmen der vorliegenden Erfindung bezeichnet der Begriff Polyvinylalkohol(co)polymer ein statistisches Copolymer oder Blockcopolymer, welches Polymerbausteine der allgemeinen Formel I enthält, oder ein Homopolymer, welches aus Polymerbausteinen der allgemeinen Formel I besteht, wobei erfindungsgemäß die Polyvinylalkoholcopolymeren von Vorteil sind, und deshalb bevorzugt angewandt werden. -[-C(R 1 ) 2 -C(R 1 )(OH)-]-   (I) In the context of the present invention, the term polyvinyl alcohol (co) polymer denotes a random copolymer or block copolymer which contains polymer units of the general formula I, or a homopolymer which consists of polymer units of the general formula I, the polyvinyl alcohol copolymers being advantageous according to the invention, and therefore are preferred. - [- C (R 1 ) 2 -C (R 1 ) (OH) -] - (I)

In den erfindungsgemäß zu verwendenden Polyvinylalkohol(co)polymeren können die Polymerbausteine I Kopf-Kopf- oder Kopf-Schwanz-verknüpft sein. Vorteilhafterweise sind die Polymerbausteine I in weitaus überwiegendem Maße Kopf-Schwanz-verknüpft.In the polyvinyl alcohol (co) polymers to be used according to the invention the polymer building blocks I be linked head-to-head or head-to-tail. The polymer building blocks I are advantageously to a far predominant extent Head and tail linked.

In der allgemeinen Formel I steht die Variable R1 für Wasserstoffatome oder für substituierte oder unsubstituierte Alkyl-, Cycloalkyl-, Alkylcycloalkyl-, Cycloalkylalkyl-, Aryl-, Alkylaryl-, Cycloalkylaryl- Arylalkyl- oder Arylcycloalkylreste.In the general formula I, the variable R 1 stands for hydrogen atoms or for substituted or unsubstituted alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl or arylcycloalkyl radicals.

Beispiele geeigneter Alkylreste sind Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, iso-Butyl, tert.-Butyl, Amyl, Hexyl oder 2-Ethylhexyl.Examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, amyl, hexyl or 2-ethylhexyl.

Beispiele geeigneter Cycloalkylreste sind Cyclobutyl, Cyclopentyl oder Cyclohexyl.Examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl or cyclohexyl.

Beispiele geeigneter Alkylcycloalkylreste sind Methylencyclohexan, Ethylencyclohexan oder Propan-1,3-diyl-cyclohexan.Examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, Ethylene cyclohexane or propane-1,3-diyl-cyclohexane.

Beispiele geeigneter Cycloalkylalkylreste sind 2-, 3- oder 4-Methyl-, -Ethyl-, - Propyl- oder -Butylcyclohex-1-yl.Examples of suitable cycloalkylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, - Propyl- or -butylcyclohex-1-yl.

Beispiele geeigneter Arylreste sind Phenyl, Naphthyl oder Biphenylyl.Examples of suitable aryl radicals are phenyl, naphthyl or biphenylyl.

Beispiele geeigneter Alkylarylreste sind Benzyl-, Ethylen- oder Propan-1,3-diylbenzol.Examples of suitable alkylaryl radicals are benzyl, ethylene or propane-1,3-diylbenzene.

Beispiele geeigneter Cycloalkylarylreste sind 2-, 3-, oder 4-Phenylcyclohex-1-yl.Examples of suitable cycloalkylaryl radicals are 2-, 3- or 4-phenylcyclohex-1-yl.

Beispiele geeigneter Arylalkylreste sind 2-, 3- oder 4-Methyl-, -Ethyl-, -Propyl- oder -Butylphen-1-yl.Examples of suitable arylalkyl radicals are 2-, 3- or 4-methyl-, -ethyl-, -propyl- or -Butylphen-1-yl.

Beispiele geeigneter Arylcycloalkylreste sind 2-, 3- oder 4-Cyclohexylphen-1-yl. Examples of suitable arylcycloalkyl radicals are 2-, 3- or 4-cyclohexylphen-1-yl.

Die vorstehend beschriebenen Reste R1 können substituiert sein. Hierzu können elektronenziehende oder elektronenschiebende Atome oder organische Reste verwendet werden.The radicals R 1 described above can be substituted. For this purpose, electron-withdrawing or electron-donating atoms or organic radicals can be used.

Beispiele geeigneter Substitutienten sind Halogenatome, insbesondere Chlor und Fluor, Nitrilgruppen, Nitrogruppen, partiell oder vollständig halogenierte, insbesondere chlorierte und/oder fluorierte, Alkyl-, Cycloalkyl-, Alkylcycloalkyl-, Cycloalkylalkyl-, Aryl-, Alkylaryl-, Cycloalkylaryl- Arylalkyl- und Arylcycloalkylreste, inclusive der vorstehend beispielhaft genannten, insbesondere tert.-Butyl; Aryloxy-, Alkyloxy- und Cycloalkyloxyreste, insbesondere Phenoxy, Naphthoxy, Methoxy, Ethoxy, Propxy, Butyloxy oder Cyclohexyloxy; Arylthio-, Alkylthio- und Cycloalkylthioreste, insbesondere Phenylthio, Naphthylthio, Methylthio, Ethylthio, Propylthio, Butylthio oder Cyclohexylthio; Hydroxylgruppen; und/oder primäre, sekundäre und/oder tertiäre Aminogruppen, insbesondere Amino, N-Methylamino, N-Ethylamino, N-Propylamino, N-Phenylamino, N-Cyclohexylamino, N,N-Dimethylamino, N,N-Diethylamino, N,N-Dipropylamino, N,N-Diphenylamino, N,N-Dicyclohexylamino, N-Cyclohexyl-N-methylamino oder N-Ethyl-N-methylamino.Examples of suitable substitutes are halogen atoms, especially chlorine and Fluorine, nitrile groups, nitro groups, partially or fully halogenated, in particular chlorinated and / or fluorinated, alkyl, cycloalkyl, alkylcycloalkyl, Cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and Arylcycloalkyl radicals, including those mentioned above by way of example, in particular tert-butyl; Aryloxy, alkyloxy and cycloalkyloxy radicals, in particular phenoxy, Naphthoxy, methoxy, ethoxy, propxy, butyloxy or cyclohexyloxy; Arylthio, Alkylthio and cycloalkylthio radicals, in particular phenylthio, naphthylthio, Methylthio, ethylthio, propylthio, butylthio or cyclohexylthio; Hydroxyl groups; and / or primary, secondary and / or tertiary amino groups, especially amino, N-methylamino, N-ethylamino, N-propylamino, N-phenylamino, N-cyclohexylamino, N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-diphenylamino, N, N-dicyclohexylamino, N-cyclohexyl-N-methylamino or N-ethyl-N-methylamino.

Erfindungsgemäß ist es von Vorteil, wenn es sich bei den Resten R1 weitaus überwiegend um Wasserstoffatome handelt, d. h., daß die anderen Reste R1 nur in einem untergeordneten Anteil vorhanden sind. Im Rahmen der vorliegenden Erfindungen bezeichnet der Begriff ''untergeordneter Anteil" einen Anteil, der das anwendungstechnische Eigenschaftsprofil der Polyvinylalkohol(co)polymeren, insbesondere ihre Wasserlöslichkeit, in vorteilhafter Weise variiert und nicht verschlechtert oder gar völlig verändert. Besondere Vorteile resultieren, wenn es sich bei den Resten R1 ausschließlich um Wasserstoffatome handelt, d. h., daß sich die Polymerbausteine I von dem hypothetischen Polyvinylalkohol-ableiten. Demgemäß werden Polyvinylalkohol(co)polymere, die diese Polymerbausteine I enthalten, besonders bevorzugt verwendet.According to the invention, it is advantageous if the radicals R 1 are predominantly hydrogen atoms, that is to say that the other radicals R 1 are only present in a minor proportion. In the context of the present inventions, the term “subordinate portion” denotes a portion which advantageously varies the application properties profile of the polyvinyl alcohol (co) polymers, in particular their water solubility, and does not deteriorate or even completely change them. Special advantages result if they change the radicals R 1 are exclusively hydrogen atoms, that is to say that the polymer building blocks I are derived from the hypothetical polyvinyl alcohol. Accordingly, polyvinyl alcohol (co) polymers which contain these polymer building blocks I are used with particular preference.

Neben den Polymerbausteinen I enthalten die erfindungsgemäß zu verwendenden Polyvinylalkoholcopolymeren insbesondere noch Polymerbausteine der allgemeine Formel II. -[-C(R 1 ) 2 -C(R 1 )(OC(O)R 2 )-]-   (II) In addition to the polymer building blocks I, the polyvinyl alcohol copolymers to be used according to the invention also contain, in particular, polymer building blocks of the general formula II. - [- C (R 1 ) 2 -C (R 1 ) (OC (O) R 2 ) -] - (II)

In der allgemeinen Formel II haben die Reste R1 die vorstehend angegebene Bedeutung, wobei auch hier Wasserstoffatome von besonderem Vorteil sind und deshalb besonders bevorzugt angewandt werden. Die Reste R2 stehen für Alkylreste mit eins bis zehn Kohlenstoffatomen, vorzugsweise Methyl, Ethyl, Propyl, Isopropyl, n-Butyl, iso-Butyl, tert.-Butyl, Amyl, Hexyl oder 2-Ethylhexyl, besonders bevorzugt Methyl. Demgemäß leiten sich die besonders bevorzugten Polymerbausteine II von Vinylacetat ab. Hierbei können die Polymerbausteine II Kopf-Kopf- oder Kopf-Schwanz-verknüpft sein. Vorteilhafterweise sind die Polymerbausteine II in weitaus überwiegendem Maße Kopf-Schwanz-verknüpft.In the general formula II, the radicals R 1 have the meaning given above, hydrogen atoms also being of particular advantage here and therefore being used with particular preference. The radicals R 2 represent alkyl radicals with one to ten carbon atoms, preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl or 2-ethylhexyl, particularly preferably methyl. Accordingly, the particularly preferred polymer building blocks II are derived from vinyl acetate. Here, the polymer building blocks II can be linked head-to-head or head-to-tail. Advantageously, the polymer building blocks II are by far predominantly head-to-tail linked.

Darüber hinaus können die Polyvinylalkoholcopolymeren noch weitere übliche und bekannte ethylenisch ungesättigte Monomere wie

  • im wesentlichen säuregruppenfreien (Meth)acrylsäureester,
  • Monomere, welche mindestens eine Hydroxylgruppe pro Molekül tragen und im wesentlichen säuregruppenfrei sind, wie Hydroxyalkylester der Acrylsäure, Methacrylsäure oder einer anderen alpha,beta-olefinisch ungesättigten Carbonsäure, die sich von einem Alkylenglykol ableiten, das mit der Säure verestert ist, oder die durch Umsetzung der alpha,beta-olefinsich ungesättigten Carbonsäure mit einem Alkylenoxid erhältlich sind,
  • Monomere, welche mindestens eine Säuregruppe, die in die entsprechende Säureaniongruppe überführbar ist, pro Molekül tragen,
  • Vinylester von in alpha-Stellung verzweigten Monocarbonsäuren mit 5 bis 18 Kohlenstoffatomen im Molekül,
  • Umsetzungsprodukte aus Acrylsäure und/oder Methacrylsäure mit dem Glycidylester einer in alpha-Stellung verzweigten Monocarbonsäure mit 5 bis 18 C-Atomen je Molekül,
  • cyclische und/oder acyclische Olefine wie Ethylen, Propylen, But-1-en, Pent-1-en, Hex-1-en, Cyclohexen, Cyclopenten, Norbonen, Butadien, Isopren, Cylopentadien und/oder Dicyclopentadien, insbesondere Ethylen,
  • (Meth)Acrylsäureamide
  • Epoxidgruppen enthaltende Monomere wie die Glycidylester ethylenisch ungesättigter Carbonsäuren,
  • vinylaromatische Kohlenwasserstoffe,
  • Nitrile,
  • Vinylverbindungen, insbesondere Vinyl- und/oder Vinylidendihalogenide, N-Vinylpyrrolidon oder Vinylether,
  • Allylverbindungen, insbesondere Allylether und -ester.
In addition, the polyvinyl alcohol copolymers can also contain other customary and known ethylenically unsaturated monomers such as
  • essentially acid group-free (meth) acrylic acid esters,
  • Monomers which carry at least one hydroxyl group per molecule and are essentially free of acid groups, such as hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta-olefinically unsaturated carboxylic acid, which are derived from an alkylene glycol which is esterified with the acid, or which are obtained by reaction the alpha, beta-olefin unsaturated carboxylic acid can be obtained with an alkylene oxide,
  • Monomers which carry at least one acid group per molecule that can be converted into the corresponding acid anion group,
  • Vinyl esters of alpha-branched monocarboxylic acids with 5 to 18 carbon atoms in the molecule,
  • Reaction products of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid branched in the alpha position and having 5 to 18 carbon atoms per molecule,
  • cyclic and / or acyclic olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, cyclohexene, cyclopentene, norbonene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene, in particular ethylene,
  • (Meth) acrylic acid amides
  • Monomers containing epoxy groups such as the glycidyl esters of ethylenically unsaturated carboxylic acids,
  • vinyl aromatic hydrocarbons,
  • Nitriles,
  • Vinyl compounds, in particular vinyl and / or vinylidene dihalides, N-vinylpyrrolidone or vinyl ethers,
  • Allyl compounds, especially allyl ethers and esters.

Sofern diese Monomeren mit verwendet werden, sind sie in den erfindungsgemäß zu verwendenden Polyvinylalkoholcopolymeren nur in einem untergeordneten Anteil enthalten, wobei dieser Begriff auch hier in dem vorstehend erläuterten Sinne angewandt wird. Von diesen Monomeren bieten die acyclischen Olefme, insbesondere Ethylen und Propylen, insbesondere Ethylen, besondere Vorteile und werden deshalb im Bedarfsfall bevorzugt verwendet.If these monomers are also used, they are to be used according to the invention using polyvinyl alcohol copolymers only in a minor proportion included, this term also here in the sense explained above is applied. Of these monomers, the acyclic olefins offer in particular ethylene and propylene, in particular ethylene, particular advantages and are therefore preferably used if necessary.

Vorteilhafterweise weisen die erfindungsgemäß zu verwendenden Polyvinylalkohol(co)polymeren einen Polymerisationsgrad von 100 bis 20.000, bevorzugt 200 bis 15.000, besonders bevorzugt 300 bis 12.000 und insbesondere 400 bis 10.000 auf.Advantageously, those to be used according to the invention have Polyvinyl alcohol (co) polymers have a degree of polymerization of 100 to 20,000, preferably 200 to 15,000, particularly preferably 300 to 12,000 and in particular 400 up to 10,000.

Vorteilhafterweise liegt der Gehalt an Polymerbausteinen I in den Polyvinylalkoholcopolymeren bei 50 bis 99,9, bevorzugt 60 bis 99,9, besonders bevorzugt 70 bis 99 und insbesondere 80 bis 99 Mol-%.The content of polymer building blocks I is advantageously in the Polyvinyl alcohol copolymers at 50 to 99.9, preferably 60 to 99.9, especially preferably 70 to 99 and in particular 80 to 99 mol%.

Im Rahmen der vorliegenden Erfindung bieten die Polyvinylalkoholcopolymere, die die besonders vorteilhaften Polymerbausteine I und II enthalten ganz besondere Vorteile und werden deshalb erfindungsgemäß ganz besonders bevorzugt verwendet. Diese Polyvinylalkoholcopolymeren werden von der Fachwelt auch kurz als Polyvinylalkohole bezeichnet.In the context of the present invention, the polyvinyl alcohol copolymers offer the particularly advantageous polymer building blocks I and II contain very special ones Advantages and are therefore used very particularly preferably according to the invention. These polyvinyl alcohol copolymers are also known in the art for short Called polyvinyl alcohols.

Bekanntermaßen sind die Polyvinylalkohole nicht durch direkte Polymerisationsverfahren zugänglich, sondern werden über polymeranaloge Reaktionen durch Hydrolyse von Polyvinylacetat hergestellt. Besonders vorteilhafte, handelsübliche Polyvinylalkohole weisen Molekulargewichte von 10.000 bis 500.000 Dalton, vorzugsweise 15.000 bis 320.000 Dalton und insbesondere 20.0000 bis 300.000 Dalton auf. Ganz besonders vorteilhafte, handelsübliche Polyvinylalkohole weisen dabei einen Hydrolysegrad von 98 bis 99 oder 87 bis 89 Mol-% auf.It is known that the polyvinyl alcohols are not by direct Polymerization processes are accessible, but are based on polymer analogs Reactions produced by hydrolysis of polyvinyl acetate. Particularly advantageous Commercial polyvinyl alcohols have molecular weights of 10,000 to 500,000 Daltons, preferably 15,000 to 320,000 Daltons and especially 20,000 to 300,000 daltons. Very particularly advantageous, commercially available polyvinyl alcohols have a degree of hydrolysis of 98 to 99 or 87 to 89 mol%.

Der Vinylalkoholanteil läßt sich beispielsweise indirekt über die Esterzahl nach DIN 53401 bestimmen, nämlich indem der verbleibende Anteil an Vinylacetat nach der Hydrolyse mittels der Esterzahl ermittelt wird.The vinyl alcohol content can be determined, for example, indirectly via the DIN ester number 53401 determine, namely by the remaining proportion of vinyl acetate after the Hydrolysis is determined by means of the ester number.

Die Wasserlöslichkeit dieser Polyvinylalkohole kann durch die nachträgliche polymeranaloge Modifizierung mit Aldehyden in einem weiten Bereichen variiert werden. Bekanntermaßen bilden sich bei dieser Umsetzung cyclische Acetale. Beispiele geeigneter acetalisierter Polyvinylalkohole sind aus der Patentschrift DE-A-196 18 379 bekannt.The water solubility of these polyvinyl alcohols can be reduced by the subsequent polymer-analogous modification with aldehydes varies within a wide range will. It is known that cyclic acetals are formed in this reaction. Examples of suitable acetalized polyvinyl alcohols are from patent DE-A-196 18 379 known.

Überraschenderweise wird mit dem Zusatz des einfach herstellbaren und auf einfache Weise als Additiv dem Elektrotauchlackbad unmittelbar zugebbaren Polyvinylalkohol(co)polymeren, insbesondere Polyvinylalkoholen, ein allen Anforderungen genügender Kantenschutz und eine sehr gute Kontaminationsbeständigkeit, insbesondere gegen Öl, erreicht. Ebenso ist der Verlauf hervorragend. Es hat sich zudem gezeigt, daß nur sehr geringe Mengen an Polyvinylalkohol(co)polymer als Zusatz benötigt werden, was zudem zu einem beachtlichen Kostenvorteil gegenüber den den Kantenschutz verbessernden Zusätzen aus dem Stand der Technik führt.Surprisingly, with the addition of the easy to manufacture and easy to use Way as an additive to the electrodeposition paint bath Polyvinyl alcohol (co) polymers, especially polyvinyl alcohols, all Edge protection that meets requirements and a very good one Contamination resistance, especially against oil, achieved. The same is true of the course outstanding. It has also been shown that only very small amounts of Polyvinyl alcohol (co) polymer are required as an additive, which also leads to a considerable cost advantage compared to the additives that improve the edge protection from the state of the art.

Im Rahmen der Erfindung ist es vorteilhaft, wenn der Anteil an Polyvinylalkohol(co)polymeren, insbesondere Polyvinylalkoholen, in dem Elektrotauchlackbad 2 bis 10.000 ppm vorzugsweise 20 bis 5.000 ppm, jeweils bezogen auf das Gesamtgewicht des Elektrotauchlackbads, beträgt. Wenn das Elektrotauchlackbad Pigmente (anorganisch) in einem Anteil von mehr als 10%, bezogen auf den Festkörper des Elektrotauchlackbades, aufweist, so genügt meist der Zusatz in einer Menge von 2 bis 3.000 insbesondere 300, bis 1.500 ppm.In the context of the invention, it is advantageous if the proportion of Polyvinyl alcohol (co) polymers, especially polyvinyl alcohols, in the Electrocoating bath 2 to 10,000 ppm, preferably 20 to 5,000 ppm, each based on the total weight of the electrocoating bath. If that Electrocoating bath pigments (inorganic) in a proportion of more than 10%, based on the solids of the electrodeposition bath, then usually suffices Addition in an amount of 2 to 3,000, in particular 300 to 1,500 ppm.

Die erfindungsgemäße Verwendung ist im Rahmen aller üblichen anodischen (ATL) oder kathodischen (KTL) Elektrotauchlackbäder (ETL) vorteilhaft.The use according to the invention is within the scope of all customary anodic (ATL) or cathodic (KTL) electrodeposition paint baths (ETL) are advantageous.

Diese Elektrotauchlackbäder sind wäßrige Beschichtungsstoffe (ETL) mit einem Feststoffgehalt von insbesondere 5 bis 30 Gew.-%.These electrodeposition baths are aqueous coating materials (ETL) with a Solids content of in particular 5 to 30% by weight.

Der Feststoff der erfindungsgemäßen ETL besteht aus

  • (A) üblichen und bekannten Bindemitteln, die ionische oder in ionische Gruppen überführbare funktionelle Gruppen (a1) sowie zur chemischen Vernetzung befähigte funktionelle Gruppen (a2) tragen, wobei sie fremd- und/oder selbstvernetzend, insbesondere aber fremdvernetzend, sind;
  • (B) gegebenenfalls Vernetzungsmitteln, die komplementäre funktionelle Gruppen (b1) tragen, die mit den funktionellen Gruppen (a2) chemische Vernetzungsreaktionen eingehen können, und dann obligatorisch angewandt werden, wenn die Bindemittel (A) fremdvernetzend sind;
  • (C) übliche und bekannte Lackadditive sowie
  • (D) die vorstehend im Detail beschriebenen erfindungsgemäß zu verwendenden Polyvinylalkohol(co)polymeren, insbesondere Polyvinylalkohole.
    • The solid of the ETL according to the invention consists of
  • (A) customary and known binders which carry ionic functional groups (a1) or functional groups which can be converted into ionic groups and functional groups (a2) capable of chemical crosslinking, whereby they are externally and / or self-crosslinking, but in particular externally crosslinking;
  • (B) optionally crosslinking agents which carry complementary functional groups (b1) which can enter into chemical crosslinking reactions with the functional groups (a2) and which are then used obligatorily if the binders (A) are externally crosslinking;
  • (C) customary and known paint additives as well
  • (D) the polyvinyl alcohol (co) polymers to be used according to the invention, in particular polyvinyl alcohols, described in detail above.
    •

    Sind die Vernetzungsmittel (B) und/oder deren funktionellen Gruppen (b1) bereit in die Bindemittel (A) eingebaut, spricht man von Selbstvernetzung. Are the crosslinking agents (B) and / or their functional groups (b1) ready in the binder (A) incorporated, one speaks of self-crosslinking.

    Als komplemetäre funktionelle Gruppen (a2) der Bindemittel (A) kommen vorzugsweise Thio-, Amino-, Hydroxyl-, Carbamat-, Allophanat-, Carboxy-, und/oder (Meth)acrylatgruppen, insbesondere aber Hydroxylgruppen, und als komplementäre funktionellen Gruppen (b1) vorzugsweise Anhydrid-, Carboxy-, Epoxy-, blockierte Isocyanat-, Urethan-, Methylol-, Methylolether-, Siloxan-, Amino-, Hydroxy- und/oder beta-Hydroxyalkylamidgruppen, insbesondere aber blockierte Isocyanatgruppen in Betracht.The binders (A) come as complementary functional groups (a2) preferably thio, amino, hydroxyl, carbamate, allophanate, carboxy, and / or (meth) acrylate groups, but in particular hydroxyl groups, and as complementary functional groups (b1) preferably anhydride, carboxy, Epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, amino, Hydroxy and / or beta-hydroxyalkylamide groups, but especially blocked Isocyanate groups into consideration.

    Beispiele geeigneter ionischer oder in ionische Gruppen überführbare funktionelle Gruppen (a1) der Bindemittel (A) sind

  • (a11) funktionelle Gruppen, die durch Neutralisationsmittel und/oder Quaternisierungsmittel in Kationen überführt werden können, und/oder kationische Gruppen
    oder
  • (a12) funktionelle Gruppen, die durch Neutralisationsmittel in Anionen überführt werden können, und/oder anionische Gruppen.
    • Examples of suitable ionic functional groups (a1) of the binders (A) which can be converted into ionic groups are
  • (a11) functional groups which can be converted into cations by neutralizing agents and / or quaternizing agents, and / or cationic groups
    or
  • (a12) functional groups which can be converted into anions by neutralizing agents and / or anionic groups.
    •

    Die Bindemittel (A) mit funktionellen Gruppen (a11) werden in kathodisch abscheidbaren Elektrotauchlacken (KTL) verwendet, wogegen die Bindemittel (A) mit funktionellen Gruppen (a12) in anodischen Elektrotauchlacken (ATL) angewandt werden.The binders (A) with functional groups (a11) are in cathodic separable electrodeposition paints (KTL) are used, whereas the binders (A) with functional groups (a12) used in anodic electrodeposition paints (ATL) will.

    Beispiele geeigneter erfindungsgemäß zu verwendender funktioneller Gruppen (a11), die durch Neutralisationsmittel und/oder Quaternisierungsmittel in Kationen überführt werden können, sind primäre, sekundäre oder tertiäre Aminogruppen, sekundäre Sulfidgruppen oder tertiäre Phoshingruppen, insbesondere tertiäre Aminogruppen oder sekundäre Sulfidgruppen. Examples of suitable functional groups (a11) to be used according to the invention, those by neutralizing agents and / or quaternizing agents in cations are primary, secondary or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups, especially tertiary ones Amino groups or secondary sulfide groups.

    Beispiele geeigneter erfindungsgemäß zu verwendender kationischer Gruppen (a11) sind primäre, sekundäre, tertiäre oder tertiäre Sulfoniumgruppen oder quaternäre Phosphoniumgruppen, vorzugsweise quaternäre Ammoniumgruppen oder quaternäre Ammoniumgruppen, tertiäre Sulfoniumgruppen, insbesondere aber quaternäre Ammoniumgruppen.Examples of suitable cationic groups to be used according to the invention (a11) are primary, secondary, tertiary or tertiary sulfonium groups or quaternary Phosphonium groups, preferably quaternary ammonium groups or quaternary Ammonium groups, tertiary sulfonium groups, but especially quaternary groups Ammonium groups.

    Beispiele geeigneter erfindungsgemäß zu verwendender funktioneller Gruppen (a12), die durch Neutralisationsmittel in Anionen überführt werden können, sind Carbonsäure-, Sulfonsäure- oder Phosphonsäuregruppen, insbesondere Carbonsäuregruppen.Examples of suitable functional groups (a12) to be used according to the invention, which can be converted into anions by neutralizing agents Carboxylic acid, sulfonic acid or phosphonic acid groups, in particular Carboxylic acid groups.

    Beispiele geeigneter erfindungsgemäß zu verwendender anionischer Gruppen (a12) sind Carboxylat-, Sulfonat- oder Phosphonatgruppen, insbesondere Carboxylatgruppen.Examples of suitable anionic groups to be used according to the invention (a12) are carboxylate, sulfonate or phosphonate groups, in particular Carboxylate groups.

    Die Auswahl der Gruppen (a11) oder (a12) ist so zu treffen, daß keine störenden Reaktionen mit den funktionelle Gruppen (a2), die mit den Vernetzungsmitteln (B) reagieren können, möglich sind. Der Fachmann kann daher die Auswahl in einfacher Weise anhand seines Fachwissens treffen.The selection of the groups (a11) or (a12) is to be made so that no disturbing Reactions with the functional groups (a2) with the crosslinking agents (B) can react, are possible. The person skilled in the art can therefore make the selection in a simpler manner Wise, based on their expertise.

    Beispiele geeigneter Neutralisationsmittel für in Kationen umwandelbare funktionelle Gruppen (a11) sind anorganische und organische Säuren wie Schwefelsäure, Salzsäure, Phosphorsäure, Ameisensäure, Essigsäure, Milchsäure, Dimethylolpropionsäure oder Zitronensäure, insbesondere Ameisensäure, Essigsäure oder Milchsäure.Examples of suitable neutralizing agents for functional ones convertible to cations Groups (a11) are inorganic and organic acids such as sulfuric acid, Hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, Dimethylolpropionic acid or citric acid, especially formic acid, acetic acid or lactic acid.

    Beispiele für geeignete Neutralisationsmittel für in Anionen umwandelbare funktionelle Gruppen (a12) sind Ammoniak, Ammoniumsalze, wie beispielsweise Examples of suitable neutralizing agents for convertible into anions functional groups (a12) are ammonia, ammonium salts such as, for example

    Ammoniumcarbonat oder Ammoniumhydrogencarbonat, sowie Amine, wie z.B. Trimethylamin, Triethylamin, Tributylamin, Dimethylanilin, Diethylanilin, Triphenylamin, Dimethylethanolamin, Diethylethanolamin, Methyldiethanolamin, Triethanolamin und dergleichen.Ammonium carbonate or ammonium hydrogen carbonate, as well as amines, e.g. Trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, Triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, Triethanolamine and the like.

    Im allgemeinen wird die Menge an Neutralisationsmittel wird so gewählt, daß 1 bis 100 Äquivalente, bevorzugt 50 bis 90 Äquivalente der funktionellen Gruppen (a11) oder (a12) des Bindemittels (b1) neutralisiert werden.In general, the amount of neutralizing agent is chosen so that 1 to 100 equivalents, preferably 50 to 90 equivalents of the functional Groups (a11) or (a12) of the binder (b1) are neutralized.

    Beispiele geeigneter Bindemitel (A) für ATL sind aus der Patentschrift DE-A-28 24 418 bekannt. Hierbei handelt es sich vorzugsweise um Polyester, Epoxydharzester, Poly(meth)acrylate, Maleinatöle oder Polybutadienöle mit einem gewichtsmittleren Molekulargewicht von 300 bis 10.000 Dalton und einer Säurezahl von 35 bis 300 mg KOH/g.Examples of suitable binders (A) for ATL are from patent DE-A-2824 418 known. These are preferably polyester, epoxy resin ester, Poly (meth) acrylates, maleic oils or polybutadiene oils with a weight average Molecular weight from 300 to 10,000 Daltons and an acid number from 35 to 300 mg KOH / g.

    Beispiele geeigneter KTL sind aus den Patentschriften EP-A-0 082 291, EP-A-0 234 395, EP-A-0 227 975, EP-A-0 178 531, EP-A-333 327, EP-A-0 310 971, EP-A-0 456 270, US-A-3,922,253, EP-A-0 261 385, EP-A-0 245 786, DE-A-33 24 211, EP-A-0 414 199 oder EP-A-476 514 bekannt. Hierbei handelt es sich vorzugsweise um primäre, sekundäre, tertiäre oder quaternäre Amino- oder Ammoniumgruppen und/oder tertiäre Sulfoniumgruppen enthaltende Harze (A) mit Aminzahlen vorzugsweise zwischen 20 und 250 mg KOH/g und einem gewichtsmittleren Molekulargewicht vongsweise 300 bis 10.000 Dalton. Insbesondere werden Amino(meth)acrylatharze, Amonoepoxidharze, Aminoepoxidharze mit endständigen Doppelbindungen, Aminoepoxiharze mit primären und/oder sekundären Hydroxylgruppen, Aminopolyurethanharze, aminogruppenhaltige Polybutadienharze oder modifizierte Epoxidharz-Kohlendioxid-Amin-Umsetzungsprodukte. Examples of suitable KTL can be found in the patents EP-A-0 082 291, EP-A-0 234 395, EP-A-0 227 975, EP-A-0 178 531, EP-A-333 327, EP-A-0 310 971, EP-A-0 456 270, US-A-3,922,253, EP-A-0 261 385, EP-A-0 245 786, DE-A-33 24 211, EP-A-0 414 199 or EP-A-476 514 known. These are preferably primary, secondary, tertiary or quaternary amino or ammonium groups and / or resins (A) containing tertiary sulfonium groups and having amine numbers preferably between 20 and 250 mg KOH / g and a weight average Molecular weight from 300 to 10,000 daltons. In particular, be Amino (meth) acrylate resins, amino epoxy resins, amino epoxy resins with terminal Double bonds, aminoepoxy resins with primary and / or secondary Hydroxyl groups, amino polyurethane resins, amino group-containing polybutadiene resins or modified epoxy-carbon dioxide-amine reaction products.

    Erfindungsgemäß werden KTL und die entsprechenden Elektrotauchackbäder bevorzugt verwendet.According to the invention, KTL and the corresponding electrodeposition baths preferably used.

    Vorzugsweise enthalten die ETL Vernetzungsmittel (B).The EDL preferably contain crosslinking agents (B).

    Beispiele geeigneter Vernetzungsmittel (B) sind blockierte organische Polyisocyanate, insbesondere blockierte sogenannte Lackpolyisocyanate, mit aliphatisch, cycloaliphatisch, araliphatisch und/oder aromatisch gebundenen, blockierten Isocyanatgruppen.Examples of suitable crosslinking agents (B) are blocked organic ones Polyisocyanates, in particular blocked so-called paint polyisocyanates, with aliphatically, cycloaliphatically, araliphatically and / or aromatically bound, blocked isocyanate groups.

    Bevorzugt werden zu ihrer Herstellung Polyisocyanate mit 2 bis 5 Isocyanatgruppen pro Molekül und mit Viskositäten von 100 bis 10.000, vorzugsweise 100 bis 5000 und insbesondere 100 bis 2000 mPas (bei 23°C) eingesetzt. Außerdem können die Polyisocyanate in üblicher und bekannter Weise hydrophil oder hydrophob modifiziert sein.Polyisocyanates with 2 to 5 isocyanate groups are preferred for their preparation per molecule and with viscosities from 100 to 10,000, preferably 100 to 5000 and in particular 100 to 2000 mPas (at 23 ° C) are used. In addition, the Polyisocyanates in the customary and known manner are hydrophilic or hydrophobic be modified.

    Beispiele für geeignete Polyisocyanate sind beispielsweise in "Methoden der organischen Chemie", Houben-Weyl, Band 14/2, 4. Auflage, Georg Thieme Verlag, Stuttgart 1963, Seite 61 bis 70, und von W. Siefken, Liebigs Annalen der Chemie, Band 562, Seiten 75 bis 136, beschrieben. Beispielsweise geeignet sind auch die isocyanatgruppenhaltigen Polyurethanpräpolymere, die durch Reaktion von Polyolen mit einem Überschuß an Polyisocyanaten hergestellt werden können und die bevorzugt niederviskos sind.Examples of suitable polyisocyanates are, for example, in "Methods of organic chemistry ", Houben-Weyl, Volume 14/2, 4th edition, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70, and by W. Siefken, Liebigs Annalen der Chemie, Volume 562, pages 75 to 136. For example, the Polyurethane prepolymers containing isocyanate groups, which are produced by the reaction of polyols can be prepared with an excess of polyisocyanates and the are preferably of low viscosity.

    Weitere Beispiele geeigneter Polyisocyanate sind Isocyanurat-, Biuret-, Allophanat-, Iminooxadiazindion-, Urethan-, Harnstoff- und/oder Uretdiongruppen aufweisende Polyisocyanate. Urethangruppen aufweisende Polyisocyanate werden beispielsweise durch Umsetzung eines Teils der Isocyanatgruppen mit Polyolen, wie z.B. Trimethylolpropan und Glycerin, erhalten, Vorzugsweise werden aliphatische oder cycloaliphatische Polyisocyanate, insbesondere Hexamethylendiisocyanat, dimerisiertes und trimerisiertes Hexamethylendiisocyanat, Isophorondiisocyanat, 2-Isocyanatopropylcyclohexylisocyanat, Dicyclohexylmethan-2,4'-diisocyanat, Dicyclohexylmethan-4,4'-diisocyanat oder 1,3-Bis(isocyanatomethyl)cyclohexan (BIC), Diisocyanate, abgeleitet von Dimerfettsäuren, wie sie unter der Handelsbezeichnung DDI 1410 von der Firma Henkel vertrieben werden, 1,8-Düsocyanato-4-isocyanatomethyl-oktan, 1,7-Diisocyanato-4-isocyanatomethylheptan oder 1-Isocyanato-2-(3-isocyanatopropyl)cyclohexan oder Mischungen aus diesen Polyisocyanaten eingesetzt.Further examples of suitable polyisocyanates are isocyanurate, biuret, allophanate, Iminooxadiazinedione, urethane, urea and / or uretdione groups Polyisocyanates. Polyisocyanates containing urethane groups are, for example by reacting part of the isocyanate groups with polyols, e.g. Trimethylolpropane and glycerol, obtained, are preferably aliphatic or cycloaliphatic polyisocyanates, especially hexamethylene diisocyanate, dimerized and trimerized hexamethylene diisocyanate, isophorone diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, Dicyclohexylmethane-2,4'-diisocyanate, Dicyclohexylmethane-4,4'-diisocyanate or 1,3-bis (isocyanatomethyl) cyclohexane (BIC), diisocyanates derived from dimer fatty acids such as those under the The trade name DDI 1410 is sold by the Henkel company, 1,8-diisocyanato-4-isocyanatomethyl octane, 1,7-diisocyanato-4-isocyanatomethylheptane or 1-isocyanato-2- (3-isocyanatopropyl) cyclohexane or mixtures of these polyisocyanates are used.

    Beispiele für geeignete Blockierungsmittel zur Herstellung der blockierten Polyisocyanate (B) sind die aus der US-Patentschrift US-A-4,444,954 bekannten Blockierungsmittel wie

  • i) Phenole wie Phenol, Cresol, Xylenol, Nitrophenol, Chlorophenol, Ethylphenol, t-Butylphenol, Hydroxybenzoesäure, Ester dieser Säure oder 2,5- di-tert.-Butyl-4-hydroxytoluol;
  • ii) Lactame, wie ε-Caprolactam, δ-Valerolactam, γ-Butyrolactam oder β-Propiolactam;
  • iii) aktive methylenische Verbindungen, wie Diethylmalonat, Dimethylmalonat, Acetessigsäureethyl- oder -methylester oder Acetylaceton;
  • iv) Alkohole wie Methanol, Ethanol, n-Propanol, Isopropanol, n-Butanol, Isobutanol, t-Butanol, n-Amylalkohol, t-Amylalkohol, Laurylalkohol, Ethylenglykolmonomethylether, Ethylenglykolmonoethylether, Ethylenglykolmonobutylether, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, Propylenglykolmonomethylether, Methoxymethanol, Glykolsäure, Glykolsäureester, Milchsäure, Milchsäureester, Methylolharnstoff, Methylolmelamin, Diacetonalkohol, Ethylenchlorohydrin, Ethylenbromhydrin, 1,3-Dichloro-2-propanol, 1,4-Cyclohexyldimethanol oder Acetocyanhydrin;
  • v) Mercaptane wie Butylmercaptan, Hexylmercaptan, t-Butylmercaptan, t-Dodecylmercaptan, 2-Mercaptobenzothiazol, Thiophenol, Methylthiophenol oder Ethylthiophenol;
  • vi) Säureamide wie Acetoanilid, Acetoanisidinamid, Acrylamid, Methacrylamid, Essigsäureamid, Stearinsäureamid oder Benzamid;
  • vii) Imide wie Succinimid, Phthalimid oder Maleimid;
  • viii) Amine wie Diphenylamin, Phenylnaphthylamin, Xylidin, N-Phenylxylidin, Carbazol, Anilin, Naphthylamin, Butylamin, Dibutylamin oder Butylphenylamin;
  • ix) Imidazole wie Imidazol oder 2-Ethylimidazol;
  • x) Harnstoffe wie Harnstoff, Thioharnstoff, Ethylenharnstoff, Ethylenthioharnstoff oder 1,3-Diphenylharnstoff;
  • xi) Carbamate wie N-Phenylcarbamidsäurephenylester oder 2-Oxazolidon;
  • xii) Imine wie Ethylenimin;
  • xiii) Oxime wie Acetonoxim, Formaldoxim, Acetaldoxim, Acetoxim, Methylethylketoxim, Düsobutylketoxim, Diacetylmonoxim, Benzophenonoxim oder Chlorohexanonoxime;
  • xiv) Salze der schwefeligen Säure wie Natriumbisulfit oder Kaliumbisulfit;
  • xv) Hydroxamsäureester wie Benzylmethacrylohydroxamat (BMH) oder Allylmethacrylohydroxamat; oder
  • xvi) substituierte Pyrazole, Ketoxime, Imidazole oder Triazole; sowie
    • Examples of suitable blocking agents for preparing the blocked polyisocyanates (B) are the blocking agents known from US Pat. No. 4,444,954, such as
  • i) Phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-tert-butyl-4-hydroxytoluene;
  • ii) lactams, such as ε-caprolactam, δ-valerolactam, γ-butyrolactam or β-propiolactam;
  • iii) active methylenic compounds such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;
  • iv) alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol ether, methyl glycol monomethyl ether, diethylene glycol ether, methyl glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol ether, glycol monomethyl ether, Glycolic acid esters, lactic acid, lactic acid esters, methylol urea, methylol melamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloro-2-propanol, 1,4-cyclohexyldimethanol or acetocyanhydrin;
  • v) mercaptans such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;
  • vi) Acid amides such as acetoanilide, acetoanisidinamide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;
  • vii) imides such as succinimide, phthalimide or maleimide;
  • viii) amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
  • ix) imidazoles such as imidazole or 2-ethylimidazole;
  • x) ureas such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenylurea;
  • xi) carbamates such as phenyl N-phenylcarbamate or 2-oxazolidone;
  • xii) imines such as ethyleneimine;
  • xiii) oximes such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oxime;
  • xiv) salts of sulphurous acid such as sodium bisulfite or potassium bisulfite;
  • xv) hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or
  • xvi) substituted pyrazoles, ketoximes, imidazoles or triazoles; as
    •

    Gemische dieser Blockierungsmittel, insbesondere Dimethylpyrazol und Triazole, Malonester und Acetessigsäureester, Dimethylpyrazol und Succinimid oder Butyldiglykol und Trimethylolpropan.Mixtures of these blocking agents, especially dimethylpyrazole and triazoles, Malonic esters and acetoacetic acid esters, dimethylpyrazole and succinimide or Butyl diglycol and trimethylol propane.

    Weitere Beispiele für geeignete Vernetzungsmittel (B) sind alle bekannten aliphatischen und/oder cycloaliphatischen und/oder aromatischen Polyepoxide, beispielsweise auf Basis Bisphenol-A oder Bisphenol-F. Als Polyepoxide geeignet sind beispielsweise auch die im Handel unter den Bezeichnungen Epikote® der Firma Shell, Denacol® der Firma Nagase Chemicals Ltd., Japan, erhältlichen Polyepoxide, wie z.B. Denacol EX-411 (Pentaerythritpolyglycidylether), Denacol EX-321 (Trimethylolpropanpolyglycidylether), Denacol EX-512 (Polyglycerolpolyglycidylether) und Denacol EX-521 (Polyglycerolpolyglycidylether).Further examples of suitable crosslinking agents (B) are all known aliphatic and / or cycloaliphatic and / or aromatic polyepoxides, for example based on bisphenol-A or bisphenol-F. Suitable as polyepoxides are, for example, also those commercially available under the names Epikote® der Shell, Denacol® from Nagase Chemicals Ltd., Japan Polyepoxides, such as Denacol EX-411 (pentaerythritol polyglycidyl ether), Denacol EX-321 (trimethylolpropane polyglycidyl ether), Denacol EX-512 (polyglycerol polyglycidyl ether) and Denacol EX-521 (polyglycerol polyglycidyl ether).

    Als Vernetzungsmittel (B) können auch Tris(alkoxycarbonylamino)triazine (TACT) der allgemeinen Formel

    Figure 00200001
    eingesetzt werden.Tris (alkoxycarbonylamino) triazines (TACT) of the general formula can also be used as crosslinking agents (B)
    Figure 00200001
    can be used.

    Beispiele geeigneter Tris(alkoxycarbonylamino)triazine (B) werden in den Patentschriften US-A-4,939,213, US-A-5,084,541 oder EP-A-0 624 577 beschrieben. Insbesondere werden die Tris(methoxy-, Tris(butoxy- und/oder Tris(2-ethylhexoxycarbonylamino)triazine verwendet.Examples of suitable tris (alkoxycarbonylamino) triazines (B) are in the US-A-4,939,213, US-A-5,084,541 or EP-A-0 624 577 are described. In particular, the tris (methoxy, tris (butoxy and / or tris (2-ethylhexoxycarbonylamino) triazines) used.

    Von Vorteil sind die Methyl-Butyl-Mischester, die Butyl-2-Ethylhexyl-Mischester und die Butylester. Diese haben gegenüber dem reinen Methylester den Vorzug der besseren Löslichkeit in Polymerschmelzen und neigen auch weniger zum Auskristallisieren.The methyl-butyl mixed esters and the butyl-2-ethylhexyl mixed esters are advantageous and the butyl esters. These have the advantage over the pure methyl ester better solubility in polymer melts and also less prone to Crystallize.

    Weitere Beispiele geeigneter Vernetzungsmittel (B) sind Aminoplastharze, beispielsweise Melamin-, Guanamin-, Benzoguanamin- oder Harnstoffharze. Dabei kommen auch die üblichen und bekannten Aminoplastharze in Betracht, deren Methylol- und/oder Methoxymethylgruppen z. T. mittels Carbamat- oder Allophanatgruppen defunktionalisiert sind. Vernetzungsmittel dieser Art werden in den Patentschriften US-A-4 710 542 und EP-B-0 245 700 sowie in dem Artikel von B. Singh und Mitarbeiter "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, Band 13, Seiten 193 bis 207, beschrieben.Further examples of suitable crosslinking agents (B) are amino resins, for example melamine, guanamine, benzoguanamine or urea resins. Included The customary and known amino resins are also suitable, their Methylol and / or methoxymethyl groups e.g. T. by means of carbamate or Allophanate groups are defunctionalized. Crosslinking agents of this type are used in US-A-4 710 542 and EP-B-0 245 700 and in the article by B. Singh et al. "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry "in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193-207.

    Weitere Beispiele geeigneter Vernetzungsmittel (B) sind beta-Hydroxyalkylamide wie N,N,N',N'-Tetrakis(2-hydroxyethyl)adipamid oder N,N,N',N'-Tetrakis(2-hydroxypropyl)-adipamid.Further examples of suitable crosslinking agents (B) are beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N'-tetrakis (2-hydroxypropyl) adipamide.

    Weitere Beispiele geeigneter Vernetzungsmittel (B) sind Verbindungen mit im Mittel mindestens zwei zur Umesterung befähigten Gruppen, beispeilsweise Umsetzungsprodukte von Malonsäurediestern und Polyisocyanaten oder von Estern und Teilestern mehrwertiger Alkohole der Malonsäure mit Monoisocyanaten, wie sie der europäischen Patentschrift EP-A-0 596 460 beschrieben werden;Further examples of suitable crosslinking agents (B) are compounds with on average at least two groups capable of transesterification, for example Reaction products of malonic acid diesters and polyisocyanates or of esters and partial esters of polyhydric alcohols of malonic acid with monoisocyanates, such as them European Patent EP-A-0 596 460;

    Die Menge der Vernetzungsmittel (B) in dem erfindungsgemäßen Beschichtungsstoff oder ETL kann breit variieren und richtet sich insbesondere zum einen nach der Funktionalität der Vernetzungsmittel (B) und zum anderen nach der Anzahl der im Bindemittel (A) vorhandenen vernetzenden funktionellen Gruppen (a2) sowie nach der Vernetzungsdichte, die man erzielen will. Der Fachmann kann daher die Menge der Vernetzungsmittel (B) aufgrund seines allgemeinen Fachwissens, gegebenenfalls unter Zuhilfenahme einfacher orientierender Versuche ermitteln. Vorteilhafterweise ist das Vernetzungsmittel (B) in dem erfindungsgemäßen Beschichtungsstoff in einer Menge von 5 bis 60 Gew.-%, besonders bevorzugt 10 bis 50 Gew.-% und insbesondere 15 bis 45 Gew.-%, jeweils bezogen auf den Feststoffgehalt des erfindungsgemäßen Beschichtungsstoffs, enthalten. Hierbei empfiehlt es sich des weiteren, die Mengen an Vernetzungsmittel (B) und Bindemittel (A) so zu wählen, daß in dem erfindungsgemäßen Beschichtungsstoff das Verhältnis von funktionellen Gruppen (b1) im Vernetzungsmittel (B) und funktionellen Gruppen (a2) im Bindemittel (A) zwischen 2 : 1 bis 1 : 2, vorzugsweise 1,5 : 1 bis 1 : 1,5, besonders bevorzugt 1,2 : 1 bis 1 : 1,2 und insbesondere 1,1 : 1 bis 1 : 1,1 liegt. The amount of crosslinking agents (B) in the coating material of the invention or ETL can vary widely and is based in particular on the one hand Functionality of the crosslinking agent (B) and on the other hand according to the number of im Binder (A) existing crosslinking functional groups (a2) and after the network density that you want to achieve. The skilled person can therefore determine the amount the crosslinking agent (B) on the basis of his general technical knowledge, if appropriate determine with the help of simple, orienting experiments. Advantageously is the crosslinking agent (B) in the coating material of the invention in one Amount of 5 to 60% by weight, particularly preferably 10 to 50% by weight and in particular 15 to 45 wt .-%, each based on the solids content of the coating material according to the invention contain. It is recommended to use the further to choose the amounts of crosslinking agent (B) and binder (A) so that in the coating material of the invention the ratio of functional Groups (b1) in the crosslinking agent (B) and functional groups (a2) in Binder (A) between 2: 1 to 1: 2, preferably 1.5: 1 to 1: 1.5, especially preferably 1.2: 1 to 1: 1.2 and in particular 1.1: 1 to 1: 1.1.

    Der erfindungsgemäße Beschichtungsstoff oder ETL kann lackübliche Additive (C) in wirksamen Mengen enthalten. Beispiele geeigneter Additive (C) sind

    • organische und/oder anorganische Pigmente, Korrosionsschutzpigmente und/oder Füllstoffe wie Calciumsulfat, Bariumsulfat, Silikate wie Talk oder Kaolin, Kieselsäuren, Oxide wie Aluminiumhydroxid oder Magnesiumhydroxid, Nanopartikel, organische Füllstoffe wie Textilfasern, Cellulosefasern, Polyethylenfasern oder Holzmehl, Titandioxid, Ruß, Eisenoxid, Zinkphosphat oder Bleisilikat; diese Additive können auch über Pigmentpasten in die erfindungsgemäße ETL eingearbeitet werden, wobei als Reibharze die vorstehend beschriebenen Bindemittel (A) in Betracht kommen;
    • Radikalfänger;
    • organische Korrosionsinhibitoren;
    • Katalysatoren für die Vernetzung wie anorganische und organische Salze und Komplexe des Zinns, Bleis, Antimons, Wismuts, Eisens oder Mangans, vorzugsweise organische Salze und Komplexe des Wismuts und des Zinns, insbesondere Wismutlactat, -ethylhexanoat oder -dimethylolpropionat, Dibutylzinnoxid oder Dibutylzinndilaurat;
    • Slipadditive;
    • Polymerisationsinhibitoren;
    • Entschäumer;
    • Emulgatoren, insbesondere nicht ionische Emulgatoren wie alkoxylierte Alkanole und Polyole, Phenole und Alkylphenole oder anionische Emulgatoren wie Alkalisalze oder Ammoniumsalze von Alkancarbonsäuren, Alkansulfonsäuren, und Sulfosäuren von alkoxylierten Alkanolen und Polyolen, Phenolen und Alkylphenole;
    • Netzmittel wie Siloxane, fluorhaltige Verbindungen, Carbonsäurehalbester, Phosphorsäureester, Polyacrylsäuren und deren Copolymere oder Polurethane;
    • Haftvermittler;
    • Verlaufmittel;
    • filmbildende Hilfsmittel wie Cellulose-Derivate;
    • Flammschutzmittel;
    • organische Lösemittel;
    • niedermolekulare, oligomere und hochmolekulare Reaktivverdünner, die an der thermischen Vernetzung teilnehmen können, insbesondere Polyole wie Tricyclodecandimethanol, dendrimere Polyole, hyperverzweigte Polyester, Polyole auf der Basis von Metatheseoligomeren oder verzweigten Alkanen mit mehr als acht Kohlenstoffatomen im Molekül;
    • Antikratermittel;
    The coating material or EDL according to the invention can contain customary lacquer additives (C) in effective amounts. Examples of suitable additives (C) are
    • organic and / or inorganic pigments, anti-corrosive pigments and / or fillers such as calcium sulfate, barium sulfate, silicates such as talc or kaolin, silicic acids, oxides such as aluminum hydroxide or magnesium hydroxide, nanoparticles, organic fillers such as textile fibers, cellulose fibers, polyethylene fibers or wood flour, titanium dioxide, carbon black, iron oxide, Zinc phosphate or lead silicate; these additives can also be incorporated into the EDL according to the invention via pigment pastes, the binders (A) described above being suitable as grinding resins;
    • Radical scavengers;
    • organic corrosion inhibitors;
    • Catalysts for crosslinking such as inorganic and organic salts and complexes of tin, lead, antimony, bismuth, iron or manganese, preferably organic salts and complexes of bismuth and tin, in particular bismuth lactate, ethylhexanoate or dimethylol propionate, dibutyltin oxide or dibutyltin dilaurate;
    • Slip additives;
    • Polymerization inhibitors;
    • Defoamer;
    • Emulsifiers, in particular non-ionic emulsifiers such as alkoxylated alkanols and polyols, phenols and alkylphenols or anionic emulsifiers such as alkali salts or ammonium salts of alkanecarboxylic acids, alkanesulphonic acids, and sulphonic acids of alkoxylated alkanols and polyols, phenols and alkylphenols;
    • Wetting agents such as siloxanes, fluorine-containing compounds, carboxylic acid half-esters, phosphoric acid esters, polyacrylic acids and their copolymers or polyurethanes;
    • Adhesion promoter;
    • Leveling agent;
    • film-forming auxiliaries such as cellulose derivatives;
    • Flame retardants;
    • organic solvents;
    • low molecular weight, oligomeric and high molecular weight reactive diluents which can take part in thermal crosslinking, in particular polyols such as tricyclodecane dimethanol, dendrimeric polyols, hyperbranched polyesters, polyols based on metathesis oligomers or branched alkanes with more than eight carbon atoms in the molecule;
    • Anti-crater agents;

    Weitere Beispiele geeigneter Lackadditive werden in dem Lehrbuch "Lackadditive" von Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, beschrieben. Further examples of suitable paint additives are given in the textbook "Paint additives" described by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998.

    Die Erfindung lehrt schließlich ein Verfahren zum Lackieren elektrisch leitfähiger Substrate, bei dem (1) das elektrisch leitfähige Substrat in ein Elektrotauchlackbad gemäß der vorstehenden Ausführungen getaucht wird, (2) das Substrat als Kathode oder Anode, vorzugsweise als Kathode, geschaltet wird, (3) durch Gleichstrom ein Film auf dem Substrat abgeschieden wird, (4) das lackierte Substrat aus dem Elektrotauchlackbad entfernt wird, (5) der abgeschiedene Lackfilm eingebrannt wird und, (6) optional, anschließend an die Stufe (5) ein Füller, ein Steinschlagschutzlack und ein Unidecklack oder alternativ ein Basislack und ein Klarlack appliziert und eingebrannt werden, wobei der Basislack und der Klarlack vorzugsweise nach dem Naß-in-naß-Verfahren appliziert und eingebrannt werden.The invention finally teaches a method for painting electrically conductive Substrates in which (1) the electrically conductive substrate in an electrodeposition bath is immersed as described above, (2) the substrate as a cathode or anode, preferably as a cathode, is switched on, (3) by direct current Film is deposited on the substrate, (4) the painted substrate from the Electrodeposition paint bath is removed, (5) the deposited paint film is baked and, (6) optionally, following step (5) a filler, a stone chip protection paint and a solid top coat or, alternatively, a base coat and a clear coat are applied and are baked, the basecoat and the clearcoat preferably after Wet-on-wet process can be applied and baked.

    BeispieleExamples 1. Herstellung der Vernetzungsmittel (B)1. Preparation of the crosslinking agent (B) 1.1 Herstellung des Vernetzungsmittels (B1)1.1 Preparation of the crosslinking agent (B1)

    In einem Reaktor, der mit einem Rührer, Rückflußkühler, Innenthermometer und Inertgaseinleitung ausgestattet ist, werden 10552 Teile Isomere und höherfunktionelle Oligomere auf Basis von 4,4'-Diphenylmethandiisocyanat mit einem NCO-Equivalentgewicht von 135 g/eq (Lupranat®, Fa. BASF/ Deutschland; NCO-Funktionalität ca. 2,7; Gehalt an 2,2'- und 2,4'-Diphenylmethandüsocyanat unter 5%) unter Stickstoff-atmosphäre vorgelegt. Man gibt 18 Teile Dibutylzinndilaurat zu und tropft 9498 Teile Butyldiglykol mit einer solchen Geschwindigkeit zu, daß die Produkttemperatur unter 60°C bleibt. Gegebenenfalls muß gekühlt werden. Nach Ende der Zugabe wird die Temperatur weitere 60 min bei 60°C gehalten und ein NCO-Equivalentgewicht von 1120 g/eq bestimmt (bezogen auf Festanteile). Nach Anlösung in 7768 Teilen Methylisobutylketon werden 933 Teile geschmolzenes Trimethylolpropan in einer solchen Geschwindigkeit zugegeben, daß eine Produkttemperatur von 100°C nicht überschritten wird. Nach Zugabeende läßt man weitere 60 min nachreagieren. Bei der nachfolgenden Kontrolle sind keine NCO-Gruppen mehr nachweisbar. Man kühlt auf 65°C ab und verdünnt gleichzeitig mit 965 Teilen n-Butanol und 267 Teilen Methylisobutylketon.In a reactor equipped with a stirrer, reflux condenser, internal thermometer and Inert gas inlet is equipped, 10552 parts are isomers and higher-functional Oligomers based on 4,4'-diphenylmethane diisocyanate with an NCO equivalent weight of 135 g / eq (Lupranat®, BASF / Germany; NCO functionality approx. 2.7; Content of 2,2'- and 2,4'-diphenylmethane diisocyanate below 5%) presented under nitrogen atmosphere. 18 parts of dibutyltin dilaurate are added and drops 9498 parts of butyl diglycol at such a rate that the Product temperature remains below 60 ° C. If necessary, it must be cooled. To At the end of the addition, the temperature is kept at 60 ° C. for a further 60 minutes and is reduced NCO equivalent weight of 1120 g / eq determined (based on solids). To Dissolving in 7768 parts of methyl isobutyl ketone, 933 parts are melted Trimethylolpropane added at such a rate that a Product temperature of 100 ° C is not exceeded. After the end of the addition one leaves react for a further 60 min. There are no NCO groups in the subsequent control more verifiable. It is cooled to 65 ° C. and diluted at the same time 965 parts of n-butanol and 267 parts of methyl isobutyl ketone.

    Der Feststoffgehalt liegt bei 70,1 % (1 h bei 130°C).The solids content is 70.1% (1 h at 130 ° C.).

    1.2 Herstellung des Vernetzungsmittels (B2)1.2 Preparation of the crosslinking agent (B2)

    In einem Reaktor, der mit einem Rührer, Rückflußkühler, Innenthermometer und Inertgaseinleitung ausgestattet ist, werden 12208 Teile Isomere und höherfunktionelle Oligomere auf Basis von 4,4'-Diphenylmethandüsocyanat mit einem NCO-Equivalentgewicht von 135 g/eq (Lupranat®, Fa. BASF / Deutschland; NCO-Funktionalität ca. 2,7; Gehalt an 2,2'- und 2,4'-Diphenylmethandiisocyanat unter 5%) unter Stickstoffatmosphäre vorgelegt. Man gibt 8 Teile Dibutylzinndilaurat zu und tropft 10499 Teile Butyldiglykol mit einer solchen Geschwindigkeit zu, daß die Produkttemperatur unter 60°C bleibt Gegebenenfalls muß gekühlt werden. Nach Ende der Zugabe wird die Temperatur weitere 60 min bei 60°C gehalten und ein NCO-Equivalentgewicht von 887 g/eq bestimmt (bezogen auf Festanteile). Nach Anlösung in 4500 Teilen Methylisobutylketon werden 1293 Teile geschmolzenes Trimethylolpropan in einer solchen Geschwindigkeit zugegeben, daß eine Produkttemperatur von 100°C nicht überschritten wird. Nach Zugabeende läßt man weitere 60 min nachreagieren. Bei der nachfolgenden Kontrolle sind keine NCO-Gruppen mehr nachweisbar. Man kühlt auf 65°C ab und verdünnt gleichzeitig mit 599 Teilen n-Butanol und 893 Teilen Methylisobutylketon. In a reactor equipped with a stirrer, reflux condenser, internal thermometer and Inert gas inlet is equipped, 12,208 parts are isomers and higher-functional Oligomers based on 4,4'-diphenylmethane diisocyanate with an NCO equivalent weight of 135 g / eq (Lupranat®, BASF / Germany; NCO functionality approx. 2.7; 2,2'- and 2,4'-diphenylmethane diisocyanate content below 5%) submitted under a nitrogen atmosphere. 8 parts of dibutyltin dilaurate are added and drops 10499 parts of butyl diglycol at such a rate that the Product temperature remains below 60 ° C. It may have to be cooled. To At the end of the addition, the temperature is kept at 60 ° C. for a further 60 minutes and is reduced NCO equivalent weight of 887 g / eq determined (based on solids). To Dissolving in 4500 parts of methyl isobutyl ketone, 1293 parts are melted Trimethylolpropane added at such a rate that a Product temperature of 100 ° C is not exceeded. After the end of the addition one leaves react for a further 60 min. There are no NCO groups in the subsequent control more verifiable. It is cooled to 65 ° C. and diluted at the same time 599 parts of n-butanol and 893 parts of methyl isobutyl ketone.

    Der Feststoffgehalt liegt bei 80,5 % (1 h bei 130°C).The solids content is 80.5% (1 h at 130 ° C).

    2. Herstellung des Vorprodukts (Lösung von Diethylentriamin-diketimin in Methylisobutylketon)2. Production of the preliminary product (solution of diethylenetriamine-diketimine in methyl isobutyl ketone)

    Aus einer 70-gewichtsprozentigen Lösung von Diethylentriamin in Methylisobutylketon wird bei 110 - 140°C das Reaktionswasser azeotrop ausgekreist. Anschließend wird mit Methylisobutylketon verdünnt bis die Lösung ein Aminequivalentgewicht von 127 aufweist.From a 70 weight percent solution of diethylenetriamine in Methyl isobutyl ketone is removed azeotropically from the water of reaction at 110-140 ° C. It is then diluted with methyl isobutyl ketone until the solution is a Has amine equivalent weight of 127.

    3. Herstellung wäßriger Dispersionen, die kathodisch abscheidbare Harze (A) und ein Vernetzungsmittel (B) enthalten3. Production of aqueous dispersions, the cathodically depositable resins (A) and a crosslinking agent (B) 3.1 Herstellung der wässrigen Bindemittel-Dispersion (A/B1)3.1 Preparation of the aqueous binder dispersion (A / B1)

    In einem Reaktor, der mit einem Rührer, Rückflußkühler, Innenthermometer und Inertgaseinleitung ausgestattet ist, werden 6150 Teile Epoxidharz auf Basis von Bisphenol A mit einem Epoxy-Equivalentgewicht (EEW) von 188 zusammen mit 1400 Teilen Bisphenol A, 335 Teilen Dodecylphenol, 470 Teilen p-Kresol und 441 Teilen Xylol unter Stickstoffatmosphäre auf 125°C aufgeheizt und 10 min gerührt. Anschließend heizt man auf 130°C und gibt 23 Teile N,N-Dimethylbenzylamin zu. Bei dieser Temperatur wird der Reaktionsansatz gehalten, bis das EEW einen Wert von 880 g/eq erreicht hat.In a reactor equipped with a stirrer, reflux condenser, internal thermometer and Inert gas inlet is equipped, 6150 parts of epoxy resin are based on Bisphenol A with an epoxy equivalent weight (EEW) of 188 along with 1400 parts of bisphenol A, 335 parts of dodecylphenol, 470 parts of p-cresol and 441 parts Parts of xylene heated to 125 ° C. under a nitrogen atmosphere and stirred for 10 min. The mixture is then heated to 130 ° C. and 23 parts of N, N-dimethylbenzylamine are added. The reaction mixture is held at this temperature until the EEW has reached a value of 880 g / eq.

    Man gibt nun eine Mischung von 7097 Teilen des Vernetzungsmittels (B) und 90 Teilen des Additivs K2000 (Polyether, Fa. Byk Chemie / Deutschland) hinzu und hält bei 100°C.
    Eine halbe Stunde danach werden 211 Teile Butylglykol und 1210 Teile Isobutanol zugesetzt.    A mixture of 7097 parts of the crosslinking agent (B) and 90 parts of the additive K2000 (polyether, Byk Chemie / Germany) is then added and the mixture is kept at 100.degree.
    Half an hour later, 211 parts of butyl glycol and 1210 parts of isobutanol are added.

    Unmittelbar anschließend wird eine Mischung von 467 Teilen des Vorprodukts gemäß. 2. (Diethylentriamin-diketimin in Methylisobutylketon) und 520 Teilen Methylethanolamin und in den Reaktor gegeben und der Ansatz auf 100°C temperiert. Nach einer weiteren halben Stunde erhöht man die Temperatur auf 105°C und gibt 159 Teile N,N-Dimethylaminopropylamin zu.Immediately thereafter is a mixture of 467 parts of the intermediate according to. 2. (Diethylenetriamine diketimine in methyl isobutyl ketone) and 520 parts Methylethanolamine and added to the reactor and the batch to 100 ° C tempered. After a further half an hour, the temperature is increased to 105 ° C and adds 159 parts of N, N-dimethylaminopropylamine.

    75 Minuten nach Aminzugabe setzt man 903 Teile Plastilit® 3060 (Propylenglykolverbindung, Fa. BASF / Deutschland) zu, verdünnt mit 522 Teilen Propylenglycolphenylether (Mischung aus 1-Phenoxy-2-propanol und 2-Phenoxy-1-propanol, Fa. BASF / Deutschland), und kühlt gleichzeitig rasch auf 95°C ab. Nach 10 min werden 14821 Teile des Reaktionsgemischs in ein Dispergiergefäß überführt. Dort gibt man portionsweise unter Rühren 474 Teile Milchsäure (88%ig in Wasser), gelöst in 7061 Teilen deionisiertem Wasser zu. Anschließend wird 20 min homogenisiert, bevor mit weiteren 12600 Teilen entionisiertem Wasser in kleinen Portionen weiter verdünnt wird.75 minutes after the addition of the amine, 903 parts of Plastilit® 3060 are used (Propylene glycol compound, BASF / Germany), diluted with 522 parts Propylene glycol phenyl ether (mixture of 1-phenoxy-2-propanol and 2-phenoxy-1-propanol, BASF / Germany), and at the same time cools down rapidly to 95 ° C. After 10 minutes, 14821 parts of the reaction mixture are placed in a dispersing vessel convicted. There, 474 parts of lactic acid (88% in Water), dissolved in 7061 parts of deionized water. Then 20 min homogenized before using a further 12600 parts of deionized water in small Portions being further diluted.

    Durch Destillation im Vakuum werden die flüchtigen Lösemittel entfernt und anschließend mengengleich durch deionisiertes Wasser ersetzt.The volatile solvents are removed by distillation in vacuo and then replaced in the same amount by deionized water.

    Die Dispersion (A/B1) besitzt folgende Kennzahlen: Feststoffgehalt 33,8 % (1 Std. bei 130°C) 29,9 % (1/2 Std. bei 180°C) Basengehalt 0,71 Milliequivalente/g Festkörper(130°C) Säuregehalt 0,36 Milliequivalente/g Festkörper(130°C) pH 6,3 Teilchengröße 116 nm (Massemittel aus Photonen-Korrelations-Spektroskopie) The dispersion (A / B1) has the following key figures: Solids content 33.8% (1 hour at 130 ° C) 29.9% (1/2 hour at 180 ° C) Base content 0.71 milliequivalents / g solid (130 ° C) Acidity 0.36 milliequivalents / g solid (130 ° C) pH 6.3 Particle size 116 nm (Mass mean from photon correlation spectroscopy)

    3.2 Herstellung der wässrigen Bindemittel-Dispersion (A/B2)3.2 Preparation of the aqueous binder dispersion (A / B2)

    Die Herstellung der Bindemittel-Dispersion (A/B2) erfolgt völlig analog zur Bindemittel-Dispersion (A/B1), jedoch werden unmittelbar nach Verdünnung mit Propylenglycolphenylether 378 Teile K-KAT® XP 348 (Bismuth-2-ethylhexanoat; 25% Bismuth, Fa. King Industries, USA) unter Rühren der organischen Stufe zugemischt. Nach Abkühlung werden völlig analog zu (A/B1) 14821 Teile des Reaktionsgemischs dispergiert:The binder dispersion (A / B2) is produced in a completely analogous manner to Binder dispersion (A / B1), however, are used immediately after dilution with Propylene glycol phenyl ether 378 parts of K-KAT® XP 348 (bismuth 2-ethylhexanoate; 25% bismuth, King Industries, USA) with stirring in the organic stage mixed in. After cooling, completely analogous to (A / B1) 14821 parts of the Reaction mixture dispersed:

    Die Dispersion (A/B2) besitzt folgende Kennzahlen: Feststoffgehalt 33,9 % (1 Std. bei 130°C) 30,1 % (1/2 Std. bei 180°C) Basengehalt 0,74 Milliequivalente/g Festkörper(130°C) Säuregehalt 0,48 Milliequivalente/g Festkörper(130°C) pH 5,9 Teilchengröße 189 nm (Massemittel aus Photonen-Korrelations-Spektroskopie) The dispersion (A / B2) has the following key figures: Solids content 33.9% (1 hour at 130 ° C) 30.1% (1/2 hour at 180 ° C) Base content 0.74 milliequivalents / g solid (130 ° C) Acidity 0.48 milliequivalents / g solid (130 ° C) pH 5.9 Particle size 189 nm (Mass mean from photon correlation spectroscopy)

    3.3 Herstellung der wässrigen Bindemittel-Dispersion (A/B3)3.3 Preparation of the aqueous binder dispersion (A / B3)

    In einem Reaktor, der mit einem Rührer, Rückflußkühler, Innenthermometer und Inertgaseinleitung ausgestattet ist, werden 6824 Teile Epoxidharz auf Basis von Bisphenol A mit einem Epoxy-Equivalentgewicht (EEW) von 188 zusammen mit 1984 Teilen Bisphenol A, 2527 Teilen ethoxyliertem Bisphenol A mit einer OH-Zahl von 222 (Dianol® 265, Fa. Akzo / Niederlande) und 597 Teilen Methylisobutylketon unter Stickstoffatmosphäre auf 130°C aufgeheizt. Dann werden 16 Teile N,N-Dimethylbenzylamin zugegeben, auf 150°C aufgeheizt und ca. 30 min bei einer Temperatur zwischen 150 und 190°C gehalten. Dann wird auf 140°C heruntergekühlt. Danach werden 21 Teile N,N-Dimethylbenzylamin zugegeben und die Temperatur solange gehalten, bis das EEW einen Wert von 1120 g/eq erreicht hat.In a reactor equipped with a stirrer, reflux condenser, internal thermometer and Inert gas inlet is equipped, 6824 parts are based on epoxy resin Bisphenol A with an epoxy equivalent weight (EEW) of 188 along with 1984 parts of bisphenol A, 2527 parts of ethoxylated bisphenol A with an OH number of 222 (Dianol® 265, Akzo / Netherlands) and 597 parts of methyl isobutyl ketone heated to 130 ° C. under a nitrogen atmosphere. Then 16 parts of N, N-dimethylbenzylamine added, heated to 150 ° C and about 30 min at a Maintained temperature between 150 and 190 ° C. Then it is raised to 140 ° C cooled down. Then 21 parts of N, N-dimethylbenzylamine are added and the temperature held until the EEW has reached a value of 1120 g / eq.

    Nun gibt man 10113 Teilen des Vernetzungsmittels (B2) zu und erniedrigt die Temperatur auf 100°C. Anschließend wird eine Mischung aus 634 Teilen des Vorprodukts (Diethylentriamin-diketimin in Methylisobutylketon; vgl. Punkt 2.) und 597 Teilen Methylethanolamin und in den Reaktor gegeben und die Reaktionsmischung für eine Stunde bei 115°C gehalten, bis eine Viskosität von ca. 6 dPa.s erreicht ist (50%ige Anlösung in Methoxypropanol, Kegel/Platte-Viskosimeter bei 23°C). Dann werden 648 Teile Propylenglycolphenylether (Mischung aus 1-Phenoxy-2-propanol und 2-Phenoxy-1-propanol, Fa. BASF / Deutschland) zugegeben.
    Nach 10 min wird die gesamte Reaktionsmischung in ein Dispergiergefäß überführt. Dort gibt man portionsweise unter Rühren 609 Teile Milchsäure (88%ig in Wasser) und 152 Teile Emulgatormischung (Mischung aus 1 Teil Butylglykol und 1 Teil eines tertiären Acetylenglykols (Surfynol 104, Fa. Air Products / USA)), gelöst in 30266 Teilen entionisiertem Wasser, zu.    10113 parts of the crosslinking agent (B2) are then added and the temperature is reduced to 100.degree. A mixture of 634 parts of the precursor (diethylenetriamine-diketimine in methyl isobutyl ketone; see point 2) and 597 parts of methylethanolamine is then added to the reactor and the reaction mixture is kept at 115 ° C. for one hour until a viscosity of approx dPa.s is reached (50% solution in methoxypropanol, cone / plate viscometer at 23 ° C). 648 parts of propylene glycol phenyl ether (mixture of 1-phenoxy-2-propanol and 2-phenoxy-1-propanol, from BASF / Germany) are then added.
    After 10 minutes, the entire reaction mixture is transferred to a dispersing vessel. There, 609 parts of lactic acid (88% in water) and 152 parts of emulsifier mixture (mixture of 1 part butyl glycol and 1 part of a tertiary acetylene glycol (Surfynol 104, Air Products / USA)), dissolved in 30266 parts of deionized, are added in portions with stirring Water, too.

    Durch Destillation im Vakuum werden die flüchtigen Lösemittel entfernt und anschließend mengengleich durch deionisiertes Wasser ersetzt.The volatile solvents are removed by distillation in vacuo and then replaced in the same amount by deionized water.

    Die Dispersion (A/B3) besitzt folgende Kennzahlen: Feststoffgehalt 37,0 % (1 Std. bei 130°C) 34,1 % (1/2 Std. bei 180°C) Basengehalt 0,53 Milliequivalente/g Festkörper(130°C) Säuregehalt 0,32 Milliequivalente/g Festkörper(130°C) pH 6,6 Teilchengröße 150 nm (Massemittel aus Photonen-Korrelations-Spektroskopie) The dispersion (A / B3) has the following key figures: Solids content 37.0% (1 hour at 130 ° C) 34.1% (1/2 hour at 180 ° C) Base content 0.53 milliequivalents / g solid (130 ° C) Acidity 0.32 milliequivalents / g solid (130 ° C) pH 6.6 Particle size 150 nm (Mass mean from photon correlation spectroscopy)

    4. Herstellung wässriger Lösungen von Polyvinylalkohol(co)polymeren (D)4. Production of aqueous solutions of polyvinyl alcohol (co) polymers (D) 4.1 Herstellung einer wässrigen Lösung von Poly(vinylalkohol-co-vinylacetat) (D1)4.1 Preparation of an aqueous solution of poly (vinyl alcohol-co-vinyl acetate) (D1)

    Poly(vinylalkohol-co-vinylacetat): Mowiol® 47-88, Fa. Clariant / Deutschland Gewichtsmittlere Molmasse 228 000 Dalton Polyvinylalkohol-Gehalt 89,2% Polyvinylacetat-Gehalt 10,8% Poly (vinyl alcohol-co-vinyl acetate): Mowiol® 47-88, Clariant / Germany Weight average molar mass 228,000 daltons Polyvinyl alcohol content 89.2% Polyvinyl acetate content 10.8%

    In einem Reaktor, der mit einem Rührer, Rückflußkühler, Innenthermometer und Inertgaseinleitung ausgestattet ist, werden 28491 Teile entionisiertes Wasser bei Raumtemperatur vorgelegt. In das vorgelegte Wasser werden kontinuierlich 1500 Teile Poly(vinylalkohol-co-vinylacetat) als feines Granulat eingerührt und anschließend unter Rühren auf 80°C aufgeheizt.
    Nach Erreichen von 80°C wird das Gemisch unter Rühren zwei Stunden gehalten, wobei das Polymer vollständig gelöst ist. Darauf erfolgt Abkühlung auf 35°C.    In a reactor equipped with a stirrer, reflux condenser, internal thermometer and inert gas inlet, 28491 parts of deionized water are placed at room temperature. 1500 parts of poly (vinyl alcohol-co-vinyl acetate) as fine granules are continuously stirred into the initially charged water and then heated to 80 ° C. with stirring.
    After reaching 80 ° C., the mixture is kept stirring for two hours, the polymer being completely dissolved. This is followed by cooling to 35 ° C.

    Die viskose Lösung wird mit 9 Teilen Parmetol® K40 (Fa. Schülke und Mayr / Deutschland) gegen Bakterienbefall stabilisiert.
    Der Feststoffgehalt der Lösung liegt bei 5,0 % (1 h bei 130°C).    The viscous solution is stabilized against bacterial attack with 9 parts of Parmetol® K40 (Schülke and Mayr / Germany).
    The solids content of the solution is 5.0% (1 h at 130 ° C.).

    4.2 Herstellung einer wässrigen Lösung von Poly(vinylalkohol-covinylacetat-co-ethylen) (D2)4.2 Preparation of an aqueous solution of poly (vinyl alcohol-covinylacetate-co-ethylene) (D2)

    Poly(vinylacetat-co-ethylen): Laborprodukt, Fa. BASF AG, Deutschland Gewichtsmittlere Molmasse 239 000 Dalton Polyvinylacetat-Gehalt 92,8% Polyethylen-Gehalt 7,2% Poly (vinyl acetate-co-ethylene): Laboratory product, BASF AG, Germany Weight average molar mass 239,000 daltons Polyvinyl acetate content 92.8% Polyethylene content 7.2%

    In einem Reaktor, der mit einem Rührer, Rückflußkühler, Innenthermometer ausgerüstet ist, werden 1000 ml einer 1%igen methanolischen Natronlauge auf 50°C erwärmt. Unter Rühren wird innerhalb von 30 Minuten eine Lösung von Poly(ethylen-co-vinylacetat) in Methanol (300g in 2000 ml Methanol) zugetropft. Nach beendeter Zugabe läßt man 30 Minuten nachreagieren und isoliert den ausgefallenen Niederschlag, wäscht mit Methanol alkalifrei und trocknet im Vakuum bei ca. 40°C.In a reactor equipped with a stirrer, reflux condenser, internal thermometer is equipped, 1000 ml of a 1% methanolic sodium hydroxide solution are heated to 50.degree warmed up. While stirring, a solution of Poly (ethylene-co-vinyl acetate) in methanol (300 g in 2000 ml of methanol) was added dropwise. When the addition is complete, the reaction is allowed to continue for 30 minutes and the is isolated deposited precipitate, washed alkali-free with methanol and dried in vacuo at approx. 40 ° C.

    Das gebildete Produkt wurde charakterisiert: Poly(vinylalkohol-co-vinylacetat-co-ethylen): Gewichtsmittlere Molmasse 215 000 Dalton Polyvinylalkohol-Gehalt 83,3% Polyvinylacetat-Gehalt 9,5% Polyethylen-Gehalt 7,2% The product formed was characterized: Poly (vinyl alcohol-co-vinyl acetate-co-ethylene): Weight average molar mass 215,000 daltons Polyvinyl alcohol content 83.3% Polyvinyl acetate content 9.5% Polyethylene content 7.2%

    Analog zum Vorgehen in Pkt. 4.1 wird eine wässrige Lösung von Poly(vinylalkohol-co-vinylacetat-co-ethylen hergestellt.Analogous to the procedure in point 4.1, an aqueous solution of poly (vinyl alcohol-co-vinyl acetate-co-ethylene manufactured.

    Der Feststoffgehalt der Lösung liegt bei 5,0 % (1 h bei 130°C).The solids content of the solution is 5.0% (1 h at 130 ° C.).

    5. Herstellung der Pigmentpasten5. Production of the pigment pastes 5.1 Herstellung der grauen Pigmentpaste (P1)5.1 Production of the gray pigment paste (P1) 5.1.1 Herstellung einer Reibharzlösung mit tertiären Ammoniumgruppen5.1.1 Preparation of a grinding resin solution with tertiary ammonium groups

    Gemäß EP 0 505 445 B1, Beispiel 1.3, wird eine organisch-wässrige Reibharzlösung hergestellt, indem man in der ersten Stufe in einem Edelstahlreaktionsgefäß 2598 Teile Bisphenol-A-diglycidylether (Epoxy-Equivalentgewicht (EEW) 188 g/eq), 787 Teile Bisphenol-A, 603 Teile Dodecylphenol und 206 Teile Butylglykol in Gegenwart von 4 Teilen Triphenylphosphin bei 130□C bis zu einem EEW von 865 g/eq reagieren läßt. Während des Abkühlens wird mit 849 Teilen Butylglykol und 1534 Teilen D.E.R.® 732 (Polypropylenglykoldiglycidylether, Fa. DOW Chemikal, USA) verdünnt und bei 90°C mit 266 Teilen 2,2'-Aminoethoxyethanol und 212 Teilen N,N-Dimethylaminopropylamin weiterreagiert. Nach 2 Stunden ist die Viskosität der Harzlösung konstant (5,3 dPa.s; 40%ig in Solvenon® PM (Methoxypropanol, Fa. BASF / Deutschland); Platte-Kegel-Viskosimeter bei 23°C). Man verdünnt mit 1512 Teilen Butylglykol und teilneutralisiert die Basengruppen mit 201 Teilen Eisessig, verdünnt weiter mit 1228 Teilen entionisiertem Wasser und trägt aus.According to EP 0 505 445 B1, example 1.3, an organic-aqueous grinding resin solution is used prepared by placing 2598 Parts of bisphenol A diglycidyl ether (epoxy equivalent weight (EEW) 188 g / eq), 787 Parts of bisphenol-A, 603 parts of dodecylphenol and 206 parts of butylglycol in Presence of 4 parts triphenylphosphine at 130 □ C up to an EEW of 865 g / eq can react. During cooling, 849 parts of butyl glycol and 1534 parts of D.E.R.® 732 (polypropylene glycol diglycidyl ether, DOW Chemikal, USA) and diluted at 90 ° C with 266 parts of 2,2'-aminoethoxyethanol and 212 Parts of N, N-dimethylaminopropylamine reacted further. After 2 hours it is Viscosity of the resin solution constant (5.3 dPa.s; 40% in Solvenon® PM (Methoxypropanol, BASF / Germany); Plate-cone viscometer at 23 ° C). It is diluted with 1512 parts of butyl glycol and the base groups are partially neutralized 201 parts of glacial acetic acid, further diluted with 1228 parts of deionized water and carries the end.

    Man erhält so eine 60%ige wässrig-organische Harzlösung, deren 10%ige Verdünnung einen pH von 6,0 aufweist.This gives a 60% aqueous-organic resin solution, its 10% Dilution has a pH of 6.0.

    Die Harzlösung wird in direkter Form zur Pastenherstellung eingesetzt.The resin solution is used directly for paste production.

    5.1.2 Herstellung der Pigmentpaste5.1.2 Preparation of the pigment paste

    Dazu werden zunächst 1897 Teile Wasser und 1750 Teile der vorstehend beschriebenen Harzlösung vorgemischt. Nun werden 21 Teile Disperbyk® 110 (Fa. Byk-Chemie GmbH/ Deutschland), 14 Teile Lanco Wax® PE W 1555 (Fa. Langer & Co. / Deutschland), 42 Teile Ruß, 420 Teile Aluminium-Hydro-Silikat ASP 200 (Fa. Langer & Co. / Deutschland), 2667 Teile Titandioxid TI-PURE® R 900 (Fa. DuPont, USA) und 189 Teile Di-n-butylzinnoxid zugegeben. Die Mischung wird 30 min lang unter einem schnellaufenden Dissolverrührwerk vordispergiert. Anschließend wird die Mischung in einer Laborkleinmühle (Motor Mini Mill, Fa. Eiger Engineering Ltd., Great Britain) während 1 bis 1,5 h bis zu einer Hegmann-Feinheit von kleiner/gleich 12 µm dispergiert und mit weiterem Wasser auf Festkörper eingestellt.To this end, 1897 parts of water and 1750 parts of the above resin solution described premixed. Now 21 parts Disperbyk® 110 (Fa. Byk-Chemie GmbH / Germany), 14 parts Lanco Wax® PE W 1555 (Langer & Co. / Germany), 42 parts carbon black, 420 parts aluminum hydro-silicate ASP 200 (Fa. Langer & Co. / Germany), 2667 parts of titanium dioxide TI-PURE® R 900 (DuPont, USA) and 189 parts of di-n-butyltin oxide were added. The mixture is left for 30 minutes predispersed under a high-speed dissolver stirrer. Then will the mixture in a small laboratory mill (Motor Mini Mill, Eiger Engineering Ltd., Great Britain) for 1 to 1.5 hours up to a Hegmann fineness of less than / equal to 12 µm dispersed and adjusted to solids with more water.

    Es wird eine entmischungsstabile Pigmentpaste PI erhalten. Feststoffgehalt 60,0 % (1/2 Std. bei 180°C) A pigment paste PI which is stable to segregation is obtained. Solids content 60.0% (1/2 hour at 180 ° C)

    5.2 Herstellung der grauen Pigmentpaste (P2)5.2 Production of the gray pigment paste (P2) 5.2.1 Herstellung einer Reibharzlösung mit Sulfoniumgruppen5.2.1 Preparation of a grinding resin solution with sulfonium groups

    Es wird eine organisch-wässrige Sulfoniumreibharzlösung hergestellt, indem man in der ersten Stufe in einem Edelstahlreaktionsgefäß 2632 Teile Bisphenol-A-diglycidylether (Epoxy-Equivalentgewicht (EEW) 188 g/eq), 985 Teile Bisphenol-A, 95 Teile Nonylphenol in Gegenwart von 1 Teilen Triphenylphosphin bei 130°C bis zu einem EEW von 760 g/eq reagieren läßt Während des Abkühlens wird mit 996 Teilen 2-Butoxypropanol die Temperatur auf 80°C abgesenkt.An organic-aqueous sulfonium grating resin solution is prepared by in the first stage in a stainless steel reaction vessel 2632 parts of bisphenol A diglycidyl ether (Epoxy equivalent weight (EEW) 188 g / eq), 985 parts bisphenol-A, 95 parts of nonylphenol in the presence of 1 part of triphenylphosphine at 130 ° C to reacts to an EEW of 760 g / eq. During the cooling process, 996 Share 2-butoxypropanol, the temperature is lowered to 80 ° C.

    Anschließend werden 603 Teile Thiodiethanol (50%ig in Wasser) zugegeben und 15 min gerührt. Nach Zugabe von 661 Teilen Dimethylolpropionsäure und 152 Teilen entionisierten Wassers wird die Säurezahl bestimmt.Then 603 parts of thiodiethanol (50% in water) are added and 15 min stirred. After adding 661 parts of dimethylolpropionic acid and 152 parts The acid number is determined in deionized water.

    Die Reaktion ist abgeschlossen, wenn die Säurezahl kleiner 5 ist (mg KOH pro g Feststoff). Dann werden 10541 Teile entionisiertes Wasser stufenweise zugegeben.The reaction is complete when the acid number is less than 5 (mg KOH per g Solid). Then 10541 parts of deionized water are gradually added.

    Man erhält so eine 28%ige wässrig-organische Harzlösung (Festkörper bei 130°C, 60min : 28,0%). This gives a 28% aqueous-organic resin solution (solids at 130 ° C, 60min: 28.0%).

    Die Harzlösung wird in direkter Form zur Pastenherstellung eingesetzt.The resin solution is used directly for paste production.

    5.2.2 Herstellung einer Reibharzlösung mit quarternären Ammoniumgruppen5.2.2 Preparation of a grinding resin solution with quaternary ammonium groups

    Zuerst werden in einem Reaktor 2040 Teile Dimethylethanolamin mit 7507 Teilen 2-Ethylhexanol-mono-urethan des Toluylendiisocyanates (90%ig) versetzt, so daß die Temperatur 70°C nicht übersteigt. Dann wird mit 2199 Teilen Butylglykol angelöst und 2751 Teile Milchsäure (88%ig), sowie 2170 Teile entionisiertes Wasser zugegeben. Die Temperatur steigt auf 90°C. Nach 3 Stunden wird das Reaktionsprodukt, welches als Quatemisierungsreagenz nachfolgend dient, abgelassen.First, 2040 parts of dimethylethanolamine are mixed with 7507 parts of 2-ethylhexanol-mono-urethane in a reactor of the toluene diisocyanate (90%) added so that the Temperature does not exceed 70 ° C. Then it is partially dissolved with 2199 parts of butyl glycol and 2751 parts of lactic acid (88%) and 2170 parts of deionized water admitted. The temperature rises to 90 ° C. After 3 hours it will Reaction product, which subsequently serves as quaternization reagent, drained.

    Es wird eine organisch-wässrige Reibharzlösung mit quarternären Ammoniumgruppen hergestellt, indem man in der ersten Stufe in einem Edelstahlreaktionsgefäß 3512 Teile Bisphenol-A-diglycidylether (Epoxy-Equivalentgewicht (EEW) 188 g/eq), 1365 Teile Bisphenol-A, 128 Teile Xylol bei 130°C in Gegenwart von 4 Teilen Triphenylphosphin bis zu einem EEW von 740 g/eq reagieren läßt. Dabei wird während der Reaktion die Temperatur auf 180°C gesteigert. Es wird gekühlt und bei 125°C werden 1947 Teile 2-Ethylhexanol-monourethan des Toluyiendiisocyanates (90%ig) zugegeben. Die Temperatur wird ca. 2 Stunden gehalten, bis keine Isocyanatgruppen mehr durch IR nachweisbar sind. Nach Anlösen mit 4893 Teilen Butylglykol wird eine Temperatur von 75°C eingestellt und 3198 Teile des oben beschriebenen Quaternisierungsreagenz zugegeben.It is an organic-aqueous grinding resin solution with quaternary Ammonium groups produced by being in the first stage in one Stainless steel reaction vessel 3512 parts bisphenol A diglycidyl ether (epoxy equivalent weight (EEW) 188 g / eq), 1365 parts bisphenol-A, 128 parts xylene 130 ° C in the presence of 4 parts of triphenylphosphine up to an EEW of 740 g / eq can react. The temperature is raised to 180 ° C. during the reaction increased. It is cooled and 1947 parts of 2-ethylhexanol-monourethane are obtained at 125.degree of the toluene diisocyanate (90%) was added. The temperature is approx. 2 Held for hours until isocyanate groups are no longer detectable by IR. To Dissolving with 4893 parts of butyl glycol, a temperature of 75 ° C is set and 3198 parts of the quaternizing reagent described above were added.

    Wenn die Säurezahl kleiner 1 ist (mg KOH pro g Feststoff), wird mit 1457 Teilen Butylglykol angelöst. If the acid number is less than 1 (mg KOH per g of solid), it is 1457 parts Butyl glycol dissolved.

    Man erhält so eine 56%ige Harzlösung (Festkörper bei 130°C, 60min: 56,0%).A 56% strength resin solution is obtained in this way (solids at 130 ° C., 60 min: 56.0%).

    Die Harzlösung wird in direkter Form zur Pastenherstellung eingesetzt.The resin solution is used directly for paste production.

    5.2.3 Herstellung der Pigmentpaste5.2.3 Preparation of the pigment paste

    Dazu werden zunächst 1863 Teile Wasser und 4119 Teile der vorstehend beschriebenen Reibharzlösung mit Sulfoniumgruppen (Pkt. 5.2.1) und 422 Teile der vorstehenden Reibharzlösung mit quarternären Ammoniumgruppen (Pkt. 5.2.2) vorgemischt. Nun werden 728 Teile Aluminium-Hydro-Silikat ASP 200 (Fa. Langer & Co. / Deutschland), 185 Teile Ruß, 6142 Teile Titandioxid TI-PURE® R 900 (Fa. DuPont, USA) und 3639 Teile Di-n-butylzinnoxid zugegeben. Die Mischung wird 30 min lang unter einem schnellaufenden Dissolverrührwerk vordispergiert. Anschließend wird die Mischung in einer Laborkleinmühle (Motor Mini Mill, Fa. Eiger Engineering Ltd., Great Britain) während 1 bis 1,5 h bis zu einer Hegmann-Feinheit von kleiner/gleich 12 µm dispergiert und mit weiterem Wasser auf Festkörper eingestellt.To this end, 1863 parts of water and 4119 parts of the above described grinding resin solution with sulfonium groups (point 5.2.1) and 422 parts of Above grating resin solution with quaternary ammonium groups (point 5.2.2) premixed. 728 parts of aluminum hydro-silicate ASP 200 (Langer & Co. / Germany), 185 parts of carbon black, 6142 parts of titanium dioxide TI-PURE® R 900 (Fa. DuPont, USA) and 3639 parts of di-n-butyltin oxide were added. The mixture turns 30 Predispersed for min under a high-speed dissolver stirrer. The mixture is then in a small laboratory mill (Motor Mini Mill, Fa. Eiger Engineering Ltd., Great Britain) for 1 to 1.5 hours up to a Hegmann fineness of less than / equal to 12 µm dispersed and with more water Solid body set.

    Es wird eine entmischungsstabile Pigmentpaste (P2) erhalten. Feststoffgehalt 61,5 % (1/2 Std. bei 180°C) A pigment paste (P2) which is stable to segregation is obtained. Solids content 61.5% (1/2 hour at 180 ° C)

    6. Herstellung erfindungsgemäßer Elektrotauchlacke (ETL)6. Production of electrodeposition paints according to the invention (ETL)

    Die Anteile der Komponenten in den Elektrotauchlackbädern sind in Tab. 1, 2 und 3 aufgeführt. Es resultieren pigmentfreie und pigmentierte Elektrotauchlackbäder (ETL). The proportions of the components in the electrodeposition baths are shown in Tables 1, 2 and 3 listed. Pigment-free and pigmented electrodeposition baths result (ETL).

    Diese Elektrotauchlacke bestehen aus Mischungen jeweils einer wässrigen Dispersion (A/B) und deionisiertem Wasser. Zu den so entstandenen Mischungen wird in den ausgewiesenen Fällen Pigmentpaste (P) unter Rühren zugesetzt.These electrodeposition paints consist of mixtures of an aqueous dispersion (A / B) and deionized water. The resulting mixtures are added to the pigment paste (P) added with stirring in designated cases.

    Die Einarbeitung der wässrigen Lösungen von Polyvinylalkohol(co)polymeren (D) kann durch Zugabe zur Bindemitteldispersion (A/B) oder Pigmentpaste (P) unter Rühren erfolgen, bzw. durch nachträgliche Zugabe zur Bindemittel-Pasten-Mischung, wie im vorliegendem Fall. Grau pigmentierte Elektrotauchlacke auf Basis der Bindemittel-Dispersion (A/B1) und der Pigmentpaste (P1) Elektrotauchlack Vergleichsversuch V1 Beispiel 1 Beispiel 2 Polyvinylalkohol-(co)polymer 0 ppm 600 ppm 600 ppm Gewichtsanteile (Teile) Bindemittel-Disp. (A/B1) 491 491 491 Pigmentpaste (P1) 120 120 120 Deion. Wasser 389 377 377 Lsg des Polyvinyl-Alkohol(co)polym. (D1) 12       (D2) 12 SUMME 1000 1000 1000 Unpigmentierte Elektrotauchlacke (Klarlack) auf Basis der Bindemittel-Dispersion (A/B2) Elektrotauchlack Vergleichsversuch V2 Beispiel 3 Beispiel 4 Polyvinylalkohol-(co)polymer 0 ppm 1500 ppm 600 ppm Gewichtsanteile (Teile) Bindemittel-Disp.(A/B2) 498 498 498 Deion. Wasser 502 462 462 Lsg des Polyvinyl-Alkohol(co)polym. (D1) 40       (D2) 40 SUMME 1000 1000 1000 Grau pigmentierte Elektrotauchlacke auf Basis der Bindemittel-Dispersion (A/B3) und der Pigmentpaste (P2) Elektrotauchlack Vergleichsversuch V3 Beispiel 5 Beispiel 6 Polyvinylalkohol-Copolymer 0 ppm 600 ppm 600 ppm Gewichtsanteile (Teile) Bindemittel-Disp.(A/B3) 416 416 416 Pigmentpaste (P2) 105 105 105 Deion. Wasser 479 467 467 Lsg des Polyvinyl-Alkohol(co)polym. (D1) 12       (D2) 12 SUMME 1000 1000 1000 The aqueous solutions of polyvinyl alcohol (co) polymers (D) can be incorporated by adding to the binder dispersion (A / B) or pigment paste (P) with stirring, or by subsequent addition to the binder-paste mixture, as in the present case. Gray pigmented electrodeposition paints based on the binder dispersion (A / B1) and the pigment paste (P1) Electrodeposition paint Comparative experiment V1 example 1 Example 2 Polyvinyl alcohol (co) polymer 0 ppm 600 ppm 600 ppm Parts by weight (parts) Binder disp. (A / B1) 491 491 491 Pigment paste (P1) 120 120 120 Deion. water 389 377 377 Solution of the polyvinyl alcohol (co) polym. (D1) 12th (D2) 12th TOTAL 1000 1000 1000 Unpigmented electrocoat (clear lacquer) based on the binder dispersion (A / B2) Electrodeposition paint Comparative experiment V2 Example 3 Example 4 Polyvinyl alcohol (co) polymer 0 ppm 1500 ppm 600 ppm Parts by weight (parts) Binder disp. (A / B2) 498 498 498 Deion. water 502 462 462 Solution of the polyvinyl alcohol (co) polym. (D1) 40 (D2) 40 TOTAL 1000 1000 1000 Gray pigmented electrodeposition paints based on the binder dispersion (A / B3) and the pigment paste (P2) Electrodeposition paint Comparative experiment V3 Example 5 Example 6 Polyvinyl alcohol copolymer 0 ppm 600 ppm 600 ppm Parts by weight (parts) Binder disp. (A / B3) 416 416 416 Pigment paste (P2) 105 105 105 Deion. water 479 467 467 Solution of the polyvinyl alcohol (co) polym. (D1) 12th (D2) 12th TOTAL 1000 1000 1000

    7. Abscheidung erfindungsgemäßer Elektrotauchlacke7. Deposition of electrodeposition paints according to the invention

    Nach 5 Tagen Alterung bei Raumtemperatur wird auf einer kathodisch geschalteten Stahlprüftafel mit 150 ohm Vorwiderstand abgeschieden.After 5 days of aging at room temperature, a cathodic connection is made Steel test panel deposited with 150 ohm series resistor.

    Zu diesen Zweck wurden wassergespülte, zinkphosphatierte Stahlprüftafeln der Fa. Chemetall 3) (Bo26 W OC) verwendet. Die Abscheidezeit beträgt 2 min bei einer Badtemperatur von 32°C. Die Abscheidespannung wurde so gewählt, daß eine Schichtdicke des eingebrannten Lackfilms von ca. 20 µm resultiert.For this purpose, water-rinsed, zinc-phosphated steel test panels from Chemetall 3) (Bo26 W OC) was used. The deposition time is 2 minutes for one Bath temperature of 32 ° C. The deposition voltage was chosen so that a The result is a layer thickness of approx. 20 µm of the stoved paint film.

    Der abgeschiedene Lackfilm wird mit deionisiertem Wasser abgespült und 20 min lang bei 180°C eingebrannt. Die so erhaltenen eingebrannten Lackfilme wurden geprüft.The deposited paint film is rinsed off with deionized water and 20 min Baked in for a long time at 180 ° C. The baked paint films thus obtained were checked.

    Die Prüfergebnisse können den Tabellen 4 und 5 entnommen werden.The test results can be found in Tables 4 and 5.

    7.1 Ergebnis der Abscheidungen7.1 Result of the depositions

    Als Vergleichsbeispiele wurden kathodisch abscheidbare Elektrotauchlackbäder ohne Zusätze von Polyvinylalkohol(co)polymeren abgeschieden (siehe auch Pkt. 6., Tab. 1-3).Cathodically depositable electrodeposition paint baths without Additions of polyvinyl alcohol (co) polymers deposited (see also point 6., tab. 1-3).

    Die angegebenen Schichtdicken verstehen sich als Trockenfilmschichtdicken. Prüfergebnisse von Elektrotauchlackbäder auf Basis der Bindemittel- Dispersionen (A/B1) und (A/b2) mit und ohne Pigmentpaste (P1) Elektrotauchlackbäder Grau pigmentiert Unpigmentiert (Klarlack) Beispiele (s. Pkt. 6; Tab. 1 u.2) V1 1 2 V2 3 4 Bindemittel-Dispersion (A/B1) dito dito (A/B2)*) dito dito Pigmentpaste (P1) dito dito - - - PVAl-CP -Lösung (1) - (D1) (D2) - (D1) (D2) Geh. PVAI-Copolym. im Bad (2), ppm 0 600 600 0 2000 2000 Abscheidung auf zinkphosphat. Stahlprüft. (3) Schichtdicke, µm 20,7 20,9 20,2 20,6 19,2 19,3 Spannung, V 300 310 300 320 320 320 Elektrische Gütezahl (4) als Maß für die Kantenbedeckung, % 6 100 97 8 88 73 Verlauf (5) 2 3 3 2 2 3 Korrosionsschutz nach 10 Zyklen Klimawechseltest (6) Unterwanderung am Ritz, mm (7) 2,3 2,1 2,1 2,3 2,1 2,3 Flächenrost (8) 1 1 1 1 1 1 Kantenrost (9) 3 1 1 4 1 2 Korrosionsschutz nach Kantenbeschichtungsprüfungder Ford-Prüfmethode BI 127-01 (10) Zahl der Rostpunkte auf einer Klingenscheide (10) >80 19 21 >80 29 35 Ölspritzerverträglichkeit (11) nach BASF-Prüfmethode MEB0123A Verkraterte Fläche pro Gesamtfl: in % (11) >80 ≤10 ≤10 >80 ≤10 ≤10 Prüfergebnisse von Elektrotauchlackbäder auf Basis der Bindemittel-Dispersion (A/B3) mit Pigmentpaste (P2) Elektrotauchlackbäder Grau pigmentiert Beispiele (s. Pkt. 6; Tab.3) V3 5 6 Bindemittel-Dispersion (A/B3) dito dito Pigmentpaste (P2) dito dito PVAI-CP-Lösung - (D1) (D2) Gehalt PVA1-Copolym. im Bad in ppm 0 600 600 Abscheidung auf zinkphosphatierten Stahlprüftafeln Schichtdicke in µm 20,2 19,9 20,3 Spannung in V 310 310 310 Elektrische Gütezahl als Maß für die Kantenbedeckung in % 12 99 95 Verlauf 2 3 3 Korrosionsschutz nach 10 Zyklen Klimawechseltest Unterwanderung am Ritz in mm 2,6 2,4 2,4 Flächenrost 1 1 1 Kantenrost 3 1 1 Korrosionsschutz nach Kantenbeschichtungsprüfung der Ford-Prüfmethode BI 127-01 Zahl der Rostpunkte auf einer Klingenscheide >80 22 24 Ölspritzerverträglichkeit nach BASF-Prüfmethode MEB0123A Verkraterte Fläche pro Gesamtfläche in % >80 ≤10 ≤10 The specified layer thicknesses are to be understood as dry film thicknesses. Test results of electrocoating baths based on the binder dispersions (A / B1) and (A / b2) with and without pigment paste (P1) Electrocoating baths Pigmented gray Unpigmented (clear coat) Examples (see Point 6; Tab. 1 and 2) V1 1 2 V2 3 4th Binder dispersion (A / B1) dito dito (STARTING AT 2)*) dito dito Pigment paste (P1) dito dito - - - PVAl-CP solution (1) - (D1) (D2) - (D1) (D2) Go PVAI copolymes. in bath (2), ppm 0 600 600 0 2000 2000 Deposition on zinc phosphate. Steel tested. (3) Layer thickness, µm 20.7 20.9 20.2 20.6 19.2 19.3 Voltage, V 300 310 300 320 320 320 Electrical figure of merit (4) as a measure of the edge coverage,% 6th 100 97 8th 88 73 History (5) 2 3 3 2 2 3 Corrosion protection after 10 Cycles climate change test (6) Infiltration at the scratch, mm (7) 2.3 2.1 2.1 2.3 2.1 2.3 Surface grate (8) 1 1 1 1 1 1 Edge grate (9) 3 1 1 4th 1 2 Corrosion protection according to the edge coating test of the Ford test method BI 127-01 (10) Number of rust points on a blade sheath (10) > 80 19th 21st > 80 29 35 Oil splash compatibility (11) according to BASF test method MEB0123A Cratered area per total area: in% (11) > 80 ≤10 ≤10 > 80 ≤10 ≤10 Test results of electrocoating baths based on the binder dispersion (A / B3) with pigment paste (P2) Electrocoating baths Pigmented gray Examples (see point 6; table 3) V3 5 6th Binder dispersion (FROM 3) dito dito Pigment paste (P2) dito dito PVAI-CP solution - (D1) (D2) Content of PVA1-Copolym. in the bathroom in ppm 0 600 600 Deposition on zinc-phosphated steel test panels Layer thickness in µm 20.2 19.9 20.3 Voltage in V 310 310 310 Electrical figure of merit as a measure of the edge coverage in% 12th 99 95 course 2 3 3 Corrosion protection after 10 cycles of alternating climatic tests Infiltration at the scratch in mm 2.6 2.4 2.4 Surface grate 1 1 1 Edge rust 3 1 1 Corrosion protection according to the edge coating test of the Ford test method BI 127-01 Number of rust spots on a blade sheath > 80 22nd 24 Oil splash compatibility according to BASF test method MEB0123A cratered area per total area in% > 80 ≤10 ≤10

    Claims (7)

    1. Use of a water-soluble polyvinyl alcohol (co)polymer or of a mixture of polyvinyl alcohol (co)polymers as an additive in aqueous cathodic electrodeposition baths, the fraction of polyvinyl alcohol (co)polymer in the electrodeposition bath being from 20 to 10 000 ppm, based on the total weight of the electrodeposition bath.
    2. Use according to Claim 1, the polyvinyl alcohol (co)polymer being a copolymer of vinyl alcohol and ethylenically unsaturated monomers, preferably one ethylenically unsaturated monomer or two or more ethylenically unsaturated monomers, especially vinyl acetate, vinyl acetal, ethylene and/or propylene.
    3. Use according to Claim 1 or 2, the polyvinyl alcohol (co)polymer having has a vinyl alcohol fraction of from 50 to 99.9, preferably from 60 to 99.9, with particular preference from 70 to 99, and in particular from 80 to 99 mol%.
    4. Use according to one of Claims 1 to 3, the weight average molecular mass of the polyvinyl alcohol (co)polymer being from 10 000 to 500 000, preferably from 15 000 to 320 000, and in particular from 20 000 to 300 000 daltons.
    5. Use according to one of Claims 1 to 4, the fraction of polyvinyl alcohol (co)polymer in the electrodeposition bath being from 20 to 5000 ppm, and in particular from 300 to 1500 ppm, based in each case on the total weight of the electrodeposition bath.
    6. Aqueous cathodic electrodeposition bath comprising
      (A) a cathodically depositable binder,
      (B) optionally a crosslinking agent,
      (C) optionally, customary coatings additives, and
      (D) a dissolved polyvinyl alcohol (co)polymer according to one of Claims 2 to 5, the fraction of polyvinyl alcohol (co)polymer in the electrodeposition bath being from 20 to 10 000 ppm, based on the total weight of the electrodeposition bath.
    7. Method of coating electrically conductive substrates, in which
      (1) the electrically conductive substrate is dipped into an electrodeposition bath according to Claim 6,
      (2) the substrate is connected as the cathode,
      (3) a film is deposited on the substrate by means of direct current,
      (4) the coated substrate is removed from the electrodeposition bath,
      (5) the deposited coating film is baked, and,
      (6) optionally, following step (5), a primer-surfacer, and/or a stonechip protectant material and a solid-color topcoat material, or alternatively a basecoat material and a clearcoat material, are applied and baked, the basecoat material and the clearcoat material being applied and baked in particular by the wet-on-wet technique.
    EP00945845A 1999-06-30 2000-06-29 Electrodeposition bath with water-soluble polyvinyl alcohol (co)polymers Expired - Lifetime EP1192226B1 (en)

    Applications Claiming Priority (3)

    Application Number Priority Date Filing Date Title
    DE19930060A DE19930060A1 (en) 1999-06-30 1999-06-30 Electrocoating bath with water-soluble polyvinyl alcohol (co) polymers
    DE19930060 1999-06-30
    PCT/EP2000/006035 WO2001002498A1 (en) 1999-06-30 2000-06-29 Electrodeposition bath with water-soluble polyvinyl alcohol (co)polymers

    Publications (2)

    Publication Number Publication Date
    EP1192226A1 EP1192226A1 (en) 2002-04-03
    EP1192226B1 true EP1192226B1 (en) 2005-06-15

    Family

    ID=7913117

    Family Applications (1)

    Application Number Title Priority Date Filing Date
    EP00945845A Expired - Lifetime EP1192226B1 (en) 1999-06-30 2000-06-29 Electrodeposition bath with water-soluble polyvinyl alcohol (co)polymers

    Country Status (9)

    Country Link
    US (1) US6951602B1 (en)
    EP (1) EP1192226B1 (en)
    JP (1) JP5527915B2 (en)
    AT (1) ATE297967T1 (en)
    AU (1) AU5979800A (en)
    BR (1) BR0012095B1 (en)
    DE (2) DE19930060A1 (en)
    ES (1) ES2243279T3 (en)
    WO (1) WO2001002498A1 (en)

    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2019072774A1 (en) 2017-10-09 2019-04-18 Basf Coatings Gmbh Electrocoats containing at least one triazine compound
    WO2023117937A1 (en) 2021-12-21 2023-06-29 Basf Se Environmental attributes for coating materials

    Families Citing this family (34)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE10009913B4 (en) * 2000-03-01 2004-12-23 Basf Coatings Ag Process for the production of multi-layer coatings on electrically conductive substrates and their use
    DE10209396A1 (en) * 2002-03-02 2003-09-18 Basf Coatings Ag Electrocoat (ETL) free of insoluble solids
    JP2004197073A (en) * 2002-12-02 2004-07-15 Sankyo Seiki Mfg Co Ltd Electrodeposition material, motor and lens driving device
    US7930815B2 (en) 2003-04-11 2011-04-26 Avery Dennison Corporation Conductive pattern and method of making
    US20040200061A1 (en) * 2003-04-11 2004-10-14 Coleman James P. Conductive pattern and method of making
    TWI328622B (en) * 2005-09-30 2010-08-11 Rohm & Haas Elect Mat Leveler compounds
    US7381331B2 (en) * 2005-09-30 2008-06-03 General Electric Company Hydrophilic membrane and associated method
    US8389653B2 (en) * 2006-03-30 2013-03-05 Basf Corporation Method of catalyzing a reaction to form a urethane coating and a complex for use in the method
    US7374686B2 (en) * 2006-04-11 2008-05-20 Basf Corporation Electrocoat manufacturing process
    US20080289968A1 (en) * 2007-05-25 2008-11-27 Basf Corporation Method of coating a substrate including a simultaneous cure
    US8062760B2 (en) * 2008-06-19 2011-11-22 Basf Coatings Gmbh Electrocoat composition and process
    JP6375304B2 (en) 2012-11-09 2018-08-15 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツングＢＡＳＦ Ｃｏａｔｉｎｇｓ ＧｍｂＨ Method for improving paint curability of articles coated with phosphate-contaminated electrodeposition paint composition and electrodeposition paint composition
    EP3071658B1 (en) 2013-11-18 2017-12-13 BASF Coatings GmbH Two-stage method for dip coating electrically conductive substrates using a composition containing bi(iii)
    PL3083077T3 (en) 2013-12-18 2020-04-30 Basf Coatings Gmbh Method for producing a multilayer coating
    WO2015090814A1 (en) 2013-12-18 2015-06-25 Basf Coatings Gmbh Method for producing a multi-layer lacquer finish
    KR102351172B1 (en) 2013-12-18 2022-01-13 바스프 코팅스 게엠베하 METHOD FOR PRODUCING A MULTICOAT PAINT SYSTEM ON A METALLIC SUBSTRATE AND MULTICOAT PAINT SYSTEM PRODUCED THEREBY
    EP2886207A1 (en) 2013-12-18 2015-06-24 BASF Coatings GmbH Method for producing a multilayer coating
    CN107531863B (en) 2015-05-06 2022-02-08 巴斯夫涂料有限公司 Method for producing a multi-layer paint system
    RU2700867C1 (en) 2015-11-26 2019-09-23 БАСФ Коатингс ГмбХ Method of producing a multilayer paint system
    US10718059B2 (en) * 2017-07-10 2020-07-21 Rohm And Haas Electronic Materials Llc Nickel electroplating compositions with cationic polymers and methods of electroplating nickel
    CA3075644A1 (en) * 2017-10-09 2019-04-18 Owens Corning Intellectual Capital, Llc Aqueous binder compositions
    AU2018348018B2 (en) 2017-10-09 2022-09-29 Owens Corning Intellectual Capital, Llc Aqueous binder compositions
    MX2021004131A (en) 2018-10-12 2021-06-15 Basf Coatings Gmbh Method for producing a multi-layer lacquer finish via the post-additivation of an aqueous dispersion, containing polyamides and/or amide waxes, to at least one base lacquer.
    MX2022001224A (en) 2019-07-29 2022-03-02 Basf Coatings Gmbh Process for producing a multilayer coating comprising a sparkling coat layer and multilayer coating obtained from said process.
    WO2021078923A1 (en) 2019-10-23 2021-04-29 Basf Coatings Gmbh Pigmented aqueous coating composition with improved stability towards pinholes
    US11813833B2 (en) 2019-12-09 2023-11-14 Owens Corning Intellectual Capital, Llc Fiberglass insulation product
    US20210238439A1 (en) * 2019-12-30 2021-08-05 Axalta Coating Systems Ip Co., Llc Low density electrocoat composition with improved throwing power
    US20210371678A1 (en) 2020-05-28 2021-12-02 Axalta Coating Systems Ip Co., Llc Electrocoating composition
    JP7241973B2 (en) * 2020-06-23 2023-03-17 関西ペイント株式会社 Cationic electrodeposition paint composition
    JP2024510741A (en) * 2021-03-10 2024-03-11 ビーエーエスエフ コーティングス ゲゼルシャフト ミット ベシュレンクテル ハフツング Aqueous dispersion containing cationic polyvinyl alcohol-modified polymer particles and aqueous electrodeposition coating material containing the dispersion
    EP4363509A1 (en) * 2021-07-01 2024-05-08 PPG Industries Ohio Inc. Electrodepositable coating compositions
    CA3222684A1 (en) * 2021-07-01 2023-01-05 Brian Carl OKERBERG Electrodepositable coating compositions
    WO2023279080A1 (en) * 2021-07-01 2023-01-05 Ppg Industries Ohio, Inc. Electrodepositable coating compositions
    EP4186951A1 (en) 2021-11-30 2023-05-31 BASF Coatings GmbH Method for producing a multilayer coating

    Family Cites Families (51)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US3882008A (en) * 1966-09-20 1975-05-06 Nippon Soda Co Water-soluble and/or water-dispersible coating material and composition
    US3922253A (en) 1971-10-28 1975-11-25 Ppg Industries Inc Self-crosslinking cationic electrodepositable compositions
    JPS5073560A (en) * 1973-10-30 1975-06-17
    AU509166B2 (en) 1975-11-04 1980-04-24 Toyo Kohan Co. Ltd. Composite coated steel sheet
    JPS5394346A (en) 1977-01-27 1978-08-18 Shinto Paint Co Ltd Novel powder coating composition for electrodeposition
    US4134866A (en) * 1977-06-03 1979-01-16 Kansai Paint Company, Limited Aqueous cationic coating from amine-epoxy adduct, polyamide, and semi-blocked polyisocyanate, acid salt
    AT352842B (en) 1977-06-06 1979-10-10 Herberts & Co Gmbh Aqueous coating agent, especially for electro-dip painting, as well as the process for its production
    ZA796485B (en) 1978-12-11 1980-11-26 Shell Res Ltd Thermosetting resinous binder compositions,their preparation,and use as coating materials
    DE3067308D1 (en) * 1979-02-27 1984-05-10 Ici Plc Process for coating articles by electrodeposition, compositions for use in the process and coated articles
    JPS5644799A (en) 1979-09-14 1981-04-24 Mitsubishi Rayon Co Ltd Grinding method for electrodeposition coated article
    WO1981003292A1 (en) 1980-05-12 1981-11-26 Minnesota Mining & Mfg Composition for mechanically depositing heavy metallic coatings
    DE3044447C2 (en) 1980-11-26 1982-12-09 Basf Farben + Fasern Ag, 2000 Hamburg Process for coating an electrically conductive substrate connected as a cathode and aqueous dispersion therefor
    AT372099B (en) 1981-11-26 1983-08-25 Vianova Kunstharz Ag METHOD FOR PRODUCING HEAT-CURABLE, CATIONIC, WATER-DISCOVERABLE COATING AGENTS
    US4711397A (en) 1982-01-11 1987-12-08 Essex Group, Inc. Electromagnetic fuel injector having continuous flow path
    US4444954A (en) 1982-09-30 1984-04-24 The Sherwin-Williams Company Water reducible quaternary ammonium salt containing polymers
    DE3324211A1 (en) 1983-07-05 1985-01-17 Basf Farben + Fasern Ag, 2000 Hamburg HEAT-CURABLE BINDING MIXTURE
    US4870524A (en) 1984-07-06 1989-09-26 Furukawa Aluminum Co., Ltd. Substrate for rigid disk storage media
    DE3436345A1 (en) 1984-10-04 1986-04-17 Herberts Gmbh, 5600 Wuppertal CATHODICALLY DEPOSITABLE AQUEOUS ELECTRO-DIP COATING COATING AGENT AND THE USE THEREOF FOR COATING OBJECTS
    DE3518732A1 (en) 1985-05-24 1986-11-27 BASF Lacke + Farben AG, 4400 Münster WATER-DISCOVERABLE BINDING AGENTS FOR CATIONIC ELECTRO-DIP COATINGS AND METHOD FOR THEIR PRODUCTION
    DE3624454A1 (en) 1986-02-13 1987-08-20 Hoechst Ag AMINOURETHANES, METHOD FOR THEIR PRODUCTION AND THEIR USE
    DE3615810A1 (en) 1986-05-10 1987-11-12 Herberts Gmbh CATHODICALLY DEPOSITABLE AQUEOUS ELECTRODE COATING COAT AND ITS USE
    US4710542A (en) 1986-05-16 1987-12-01 American Cyanamid Company Alkylcarbamylmethylated amino-triazine crosslinking agents and curable compositions containing the same
    DE3628121A1 (en) 1986-08-19 1988-03-03 Herberts Gmbh FOREIGN CROSSLINKING COMBINATION OF BINDERS FOR WATER-DISCOVERABLE VARNISHES, CATHODICALLY DEPOSITABLE ELECTRO-SUBSTRATE COATINGS AND THE USE THEREOF
    AU590960B2 (en) 1986-09-04 1989-11-23 Nippon Paint Co., Ltd. Electrodeposition coating composition
    ZA873916B (en) 1986-09-26 1988-02-24 Inmont Basf Cationic electrodepositable resin compositions containing polyurethane resin dispersions
    DE3733552A1 (en) 1987-10-03 1989-04-13 Herberts Gmbh CATHODICALLY DETACHABLE WAFER ACID DYED COATING AGENT AND THE USE THEREOF
    US4931157A (en) 1988-02-18 1990-06-05 Ppg Industries, Inc. Epoxy resin advancement using urethane polyols and method for use thereof
    DE3809695A1 (en) * 1988-03-23 1989-10-12 Hoechst Ag HARDENERS FOR SYNTHETIC RESINS, THESE CONTAINABLE MIXTURES AND THE USE THEREOF
    US4939213A (en) 1988-12-19 1990-07-03 American Cyanamid Company Triazine crosslinking agents and curable compositions containing the same
    US5084541A (en) 1988-12-19 1992-01-28 American Cyanamid Company Triazine crosslinking agents and curable compositions
    JPH0339370A (en) * 1989-07-05 1991-02-20 Honny Chem Ind Co Ltd Dull electrodeposition coating composition
    AT394197B (en) 1989-08-23 1992-02-10 Vianova Kunstharz Ag METHOD FOR PRODUCING BINDING AGENTS FOR CATHODICALLY DEPOSITABLE PAINTS
    DE3940782A1 (en) 1989-12-09 1991-06-13 Herberts Gmbh AQUEOUS COATING AGENT FOR ELECTRIC DIP PAINTING AND ITS USE IN THE MANUFACTURE OF MULTILAYER PAINTINGS
    DE3942766A1 (en) 1989-12-23 1991-06-27 Basf Lacke & Farben PROCESS FOR COATING ELECTRICALLY CONDUCTIVE SUBSTRATES, WAESSRIGER PAINT, EPOXY AMINADDUCT AND THE USE OF THE EPOXY AMINO ADDUCT AS A REIN RESIN FOR THE MANUFACTURE OF PIGMENT PASTES
    JPH0418460A (en) 1990-05-11 1992-01-22 Kansai Paint Co Ltd Resin composition for cationic electrodeposition paint
    JPH0423873A (en) * 1990-05-18 1992-01-28 Japan Synthetic Rubber Co Ltd Composition for coating
    AT394729B (en) 1990-09-17 1992-06-10 Vianova Kunstharz Ag METHOD FOR PRODUCING CROSSLINKING COMPONENTS FOR CATHODICALLY DEPOSITABLE VARNISH BINDERS
    US5158849A (en) 1990-10-25 1992-10-27 Custom Papers Group Inc. Composition useful in transparent conductive coatings
    JPH04366123A (en) * 1991-06-12 1992-12-18 Asahi Chem Ind Co Ltd Water-base blocked isocyanate and coating composition prepared therefrom
    JP3130959B2 (en) * 1991-06-12 2001-01-31 旭化成工業株式会社 Water-based paint composition
    DE4204581A1 (en) 1992-02-15 1993-08-19 Basf Lacke & Farben METHOD FOR PAINTING ELECTRICALLY CONDUCTIVE SUBSTRATES, WAFEREN ELECTROCOATED LACQUERS, PROCESS FOR PREPARING A REFERENCE TO DISPERSION OF CROSSLINKED POLYMIC SYRINGE PARTICLES, AND DISPERSIONES MADE ACCORDING TO THIS METHOD
    DE4237490A1 (en) 1992-11-06 1994-05-11 Herberts Gmbh Coating agent and its use for the production of acid-resistant coatings
    DE4303787C1 (en) * 1993-02-10 1994-03-24 Herberts Gmbh Blemish free electrophoretic coatings - prepd by treatment of the coating in an aq polyvinyl alcohol soln prior to hardening
    JPH06248204A (en) 1993-02-26 1994-09-06 Pentel Kk Matte electrodeposition coating
    JPH06248200A (en) 1993-02-26 1994-09-06 Kansai Paint Co Ltd Heat-curable coating composition for absorption of vibration
    TW328955B (en) 1993-05-14 1998-04-01 Cytec Tech Corp Process for preparing bis- or tris-carbamate functional 1,3,5-triazines, substantially halogen contamination free crosslinker compositions and new bis-or tris-carbamate functional 1,3,5-triazines
    US5430078A (en) 1993-08-31 1995-07-04 Basf Corporation Electrodeposition coating composition comprising cellulose additive
    WO1996027034A1 (en) 1995-02-28 1996-09-06 Henkel Corporation Reducing or avoiding surface irregularities in electrophoretic painting of phosphated metal surfaces
    DE19618379A1 (en) * 1996-05-08 1997-11-13 Basf Lacke & Farben Water-dispersible epoxy resins modified with copolymers of vinyl acetate
    DE19622221A1 (en) * 1996-06-03 1997-12-04 Henkel Kgaa Process for coating electrically conductive substrates
    JP2001011201A (en) 1999-07-01 2001-01-16 Denki Kagaku Kogyo Kk Object made by vulcanization-bonding chloroprene copolymer to metal

    Cited By (4)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    WO2019072774A1 (en) 2017-10-09 2019-04-18 Basf Coatings Gmbh Electrocoats containing at least one triazine compound
    US11692105B2 (en) 2017-10-09 2023-07-04 Basf Coatings Gmbh Electrocoats containing at least one triazine compound
    WO2023117937A1 (en) 2021-12-21 2023-06-29 Basf Se Environmental attributes for coating materials
    WO2023117951A1 (en) 2021-12-21 2023-06-29 Basf Se Apparatus for generating a digital access element

    Also Published As

    Publication number Publication date
    US6951602B1 (en) 2005-10-04
    DE50010568D1 (en) 2005-07-21
    JP2003504448A (en) 2003-02-04
    WO2001002498A1 (en) 2001-01-11
    BR0012095A (en) 2002-04-02
    DE19930060A1 (en) 2001-01-11
    ATE297967T1 (en) 2005-07-15
    ES2243279T3 (en) 2005-12-01
    EP1192226A1 (en) 2002-04-03
    JP5527915B2 (en) 2014-06-25
    AU5979800A (en) 2001-01-22
    BR0012095B1 (en) 2010-11-03

    Similar Documents

    Publication Publication Date Title
    EP1192226B1 (en) Electrodeposition bath with water-soluble polyvinyl alcohol (co)polymers
    EP1246874B1 (en) Coating that contains a colloidally dispersed metallic bismuth
    US8152983B2 (en) Electrophoretic paint containing bismuth components
    US7504444B2 (en) Aqueous electrocoat materials, their use in processes for coating electrically conductive substrates, and the use of bismuth compounds in these aqueous electrocoat materials
    EP3197961B1 (en) Aqueous binder dispersions for cathodic electrodip coating
    DE3436346A1 (en) FOREIGN CROSSLINKING, EPOXY GROUP-FREE AMINO-POLY (METH) ACRYLATE RESIN, METHOD FOR THE PRODUCTION THEREOF, THE USE THEREOF, THE KTL BATH CONTAINING IT AND THE USE THEREOF FOR COATING OBJECTS
    EP1373385B1 (en) Aqueous dispersions that are free or substantially free from volatile organic compounds, and method for their production and use thereof
    DE69935679T2 (en) METHOD OF MANUFACTURING ALLOPHANATE AND COMPOSITIONS CONTAINING SUCH COMPOUNDS
    EP0135909A2 (en) Cathodically depositable aqueous electrodipping coating composition
    WO1995008597A1 (en) Electro-dipcoating paint and process for dip-coating electroconductive substrates
    DE69307436T2 (en) Cationic electrodepositable fine particles and color composition containing them
    EP1333940A2 (en) Method for producing a multilayer coating and the use thereof
    JP2024510741A (en) Aqueous dispersion containing cationic polyvinyl alcohol-modified polymer particles and aqueous electrodeposition coating material containing the dispersion
    EP1307519B1 (en) Electro immersion lacquer produced by melt emulsification
    WO2003074618A1 (en) Electrodepositable paints free from insoluble solids
    EP0653467B1 (en) Aqueous cathodic electrodeposition paint and method of coating using it
    WO1995000593A2 (en) Electrophoretic enamel and process for lacquering electroconductive substrates
    EP0644245B1 (en) Aqueous dispersions, their manufacture and use in coatings for cathodic electrodeposition
    WO2003074617A1 (en) Insoluble-solid-free electrodip coatings
    DE10018583A1 (en) Use of water soluble cellulose ethers as anti-crate ring agents in electrophoretic coatings for the production of motor vehicle bodies and parts.

    Legal Events

    Date Code Title Description
    PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

    Free format text: ORIGINAL CODE: 0009012

    17P Request for examination filed

    Effective date: 20011122

    AK Designated contracting states

    Kind code of ref document: A1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    AX Request for extension of the european patent

    Free format text: AL;LT;LV;MK;RO;SI

    17Q First examination report despatched

    Effective date: 20040216

    GRAP Despatch of communication of intention to grant a patent

    Free format text: ORIGINAL CODE: EPIDOSNIGR1

    GRAS Grant fee paid

    Free format text: ORIGINAL CODE: EPIDOSNIGR3

    GRAA (expected) grant

    Free format text: ORIGINAL CODE: 0009210

    AK Designated contracting states

    Kind code of ref document: B1

    Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: FI

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050615

    Ref country code: GB

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050615

    Ref country code: IE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050615

    Ref country code: NL

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050615

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: EP

    Ref country code: GB

    Ref legal event code: FG4D

    Free format text: NOT ENGLISH

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: LU

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050629

    Ref country code: CY

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050629

    Ref country code: AT

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050629

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: CH

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050630

    Ref country code: BE

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050630

    Ref country code: MC

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050630

    Ref country code: LI

    Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

    Effective date: 20050630

    REF Corresponds to:

    Ref document number: 50010568

    Country of ref document: DE

    Date of ref document: 20050721

    Kind code of ref document: P

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FG4D

    Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: DK

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050915

    Ref country code: SE

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050915

    Ref country code: GR

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20050915

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: PT

    Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

    Effective date: 20051124

    NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FG2A

    Ref document number: 2243279

    Country of ref document: ES

    Kind code of ref document: T3

    GBV Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed]

    Effective date: 20050615

    REG Reference to a national code

    Ref country code: IE

    Ref legal event code: FD4D

    REG Reference to a national code

    Ref country code: CH

    Ref legal event code: PL

    ET Fr: translation filed
    PLBE No opposition filed within time limit

    Free format text: ORIGINAL CODE: 0009261

    STAA Information on the status of an ep patent application or granted ep patent

    Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

    26N No opposition filed

    Effective date: 20060316

    BERE Be: lapsed

    Owner name: BASF COATINGS A.G.

    Effective date: 20050630

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 17

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 18

    REG Reference to a national code

    Ref country code: FR

    Ref legal event code: PLFP

    Year of fee payment: 19

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: IT

    Payment date: 20190624

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: FR

    Payment date: 20190625

    Year of fee payment: 20

    PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

    Ref country code: ES

    Payment date: 20190725

    Year of fee payment: 20

    Ref country code: DE

    Payment date: 20190830

    Year of fee payment: 20

    REG Reference to a national code

    Ref country code: DE

    Ref legal event code: R071

    Ref document number: 50010568

    Country of ref document: DE

    REG Reference to a national code

    Ref country code: ES

    Ref legal event code: FD2A

    Effective date: 20201006

    PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

    Ref country code: ES

    Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

    Effective date: 20200630